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# Supersymmetry theory of microphase separation in homopolymer–oligomer mixtures

## I Introduction

Surfactant–induced mesomorphic structures based on the association between flexible homopolymers and head–functionalized oligomers represent a new class of supramolecular materials. They exhibit a rich phase behavior to be an object of investigations that have attracted, during past decade, considerable attention of both experimentalists 4  – 2  and theoreticians 26 , 27 . Microphase separation is the principal property of such systems which results in the formation of ordered mesoscopic structures due to the association between the head group of the oligomer and corresponding groups of the homopolymer, on the one hand, and unfavorable polar–nonpolar interactions between the non–polar tail of the surfactant molecules and the rest of the system, on the other one.

The homopolymer–oligomer systems involve two main classes that are relevant to strong ionic bonds and weak hydrogen ones. Unlike to conventional copolymers where repulsive blocks are bonded together by covalent bonds, there are various temporary physical interactions which play a crucial role in the formation of ordered mesophases in such systems. In the ionic bonding systems the degree of association is relatively high, so that the polymer chain resembles a comb copolymer with regularly alternating oligomer side chains. At the same time, for the systems with temperature–dependent hydrogen bonds the incompatibility must not be so strong to induce separation on a macroscopic level. Here, the microphase separation results in the periodic alternation of the layers of stretched homopolymer chains surrounded by perpendicularly oriented oligomer tails (see Figure 1).

Similarly to the conventional copolymer systems, a rich variety of morphologies (lamellar, cylindrical, spherical etc.) is shown to be possible 4 . However, for the sake of simplicity we will restrict ourselves with considering lamellar morphology only.

An example of the ionic bonding systems is represented by the mixture P4VP–(DBSA)x of the homopolymer being atactic poly(4-vinyl pyridine) (P4VP) and the surfactant as dodecyl benzene sulfonic acid (DBSA). Here, owing to the very strong interaction, the temperature domain of microphase separation is not bounded from above by association effects 4 ; DbsaZn . The peculiarity of the systems of this type, being polyelectrolyte–surfactant complexes, is that the long space structure period is an increasing function of the number oligomer/monomer ratio $`x`$ (the number of DBSA–groups per one pyridine ring). More complicated behavior is inherent in the hydrogen bonded systems which were considered to study the opposite weak-bonding limit Hb  – 2 . Here, the weak interaction causes an order–disorder transition to homogeneous high–temperature state. An example of these systems is given by the mixture P4VP–(PDP)x of the same homopolymer P4VP with 3-pentadecyl phenol (PDP) being the oligomer. In this case, unlike to the ionic bonding systems, the long space period decreases with $`x`$–increase. An intermediate behavior exhibit the system P4VP-(Zn(DBS)2)x with the oligomer being zinc dodecyl benzene sulfonate Zn(DBS)2 that forms transition metal coordination complexes with the monomers of P4VP DbsaZn . Ionic bond weakening due to the absence of covalently bound charges along the homopolymer chain leads here to a non–monotonic form of the $`x`$–dependence of the long space period.

Principally important for our consideration is decreasing form of the temperature dependence of the long space period for all above systems DbsaZn 2 . However, such character of the dependence appears in hydrogen bonded systems only within a finite temperature interval bounded by the glass transition temperature $`T_g`$ from below and order–disorder transition temperature $`T_c`$ from above Hb ; 8 . Here, an increase of the oligomer/monomer ratio $`x`$ leads to a non–monotonic behavior of the temperature $`T_c`$ with a maximum near the point $`x=0.85`$, deviation from which narrows the temperature domain $`T_g÷T_c`$. This domain is the region of our interest where a purely microphase separated structure is possible. Below the glass transition temperature $`T_g`$ the crystallization of the oligomer chains occurs that causes a reduction of the overall volume of the system and a sudden decrease of the long space period 8 .

Microphase separation phenomenon had been extensively studied in the past two decades for a variety of polymer systems including random heteropolymers 21 19 . Theoretical studies of the homopolymer-oligomer mixtures, being the systems of associating polymers, were proposed by Tanaka et al. 26  and Dormidontova et al. 27  within the random phase approximation introduced by Leibler 21 . Here, the total free energy

$$F_{tot}=F_{ho}+F_{hb}$$
(1)
is written as a sum of two terms, $`F_{ho}`$ related to the non–associated homopolymer–oligomer mixture and $`F_{hb}`$ attributed to the hydrogen bonding. Then, making use of minimization principle with respect to the dependence of the free energy $`F_{tot}`$ on the average fraction of hydrogen bonds $`X`$ present in the system, permits to find the temperature dependence $`X(T)`$ and to study possible forms of phase diagrams for both macrophase and microphase separations. It turned out that this approach gives the real dependence of the long space period $`L`$ of the ordered structure on the oligomer/monomer ratio in the system, however, as the fraction of hydrogen bonds monotonically decreases with temperature, the increasing temperature dependence of $`L(T)`$ obtained is in contradiction to the experimental data 8 . This inconsistency is caused obviously by the roughness of the random phase approximation used for description of the hydrogen bonding.

To avoid this limitation, our approach is based on the above mentioned analogy between associating homopolymer–oligomer mixtures and random comb copolymers taking into account the varying number of oligomers attached to the main chain stochastically. Such a system can be analysed in terms of the random walk statistics to apply the field theoretical scheme 10  for the development of the microscopic theory. The corner stone of our approach lies in the assumption that the alternation of the homopolymer associative groups with and without oligomers attached is like the alternation of the segments of different types along the chains of a random heteropolymer to be represented as a stochastic variation of the Ising spin, for which the role of imaginary time is played by the number of chain segment $`n`$ 11 13 .

Along this line, the problem under consideration is divided into two parts, the first of which is reduced to the determination of the relation between the long space period $`L`$ and the average fraction of hydrogen bonds $`X`$, whereas the second one is focused on the determination of the frequency $`\omega =2\pi X`$ in the distribution of the oligomer heads along the homopolymer chain. The first part of the problem was studied on base of the simplest model 2  that is reduced to the treatment of the dependence $`F_{ho}(L)`$ given by the first term of the free energy (1). Corresponding consideration developed within the framework of the strong segregation limit derives to generic relation (84) for the dependence $`L(\omega )`$ (see Appendix A). In this paper, we focus on the second problem to be related to the definition of an optimal frequency $`\omega `$ that minimizes the second term of the free energy (1) within the framework of the weak segregation limit.

The formal basis of our treatment is the field theoretical scheme of stochastic systems with using the supersymmetry field 10 . Conformably to the polymers, this theory was proposed in Vilgis  and developed for the random copolymers in Refs. 11  – 13 . Our approach is based on the Martin–Siggia–Rose method of the generating functional Rose . Power and generality of the supersymmetry field scheme was demonstrated for the Sherrington–Kirkpatrick model for which it is identical to the replica approach Kurchan . The formal base of the supersymmetry is a nilpotent quantity which represents a square root of $`0`$. In this sense, the superfield is similar to the complex field, in which the imaginary unit, being square root of $`1`$, is used instead of the anticommuting nilpotent quantity being the Grassmann variable. By definition, the supersymmetry field combines commuting the boson and anticommuting fermion components into the unified mathematical construction representing a vector in the supersymmetry space. Choice of the optimal basis of the supersymmetry correlator yields in optimal way the advanced/retarded Green functions and the structure factor to obtain microscopic expression for the frequency $`\omega `$.

The paper is organized in the following manner. Section II contains initial relations of the field scheme used to write the system Lagrangian. It involves the effective potential energy whose quadratic term describes hydrogen bonding between the oligomers and the associative groups of the homopolymer chains, whereas cubic and biquadratic terms relate to the self–action effects. The principal peculiarity of our approach lies in accounting of the inhomogeneity in the distribution of oligomers along the homopolymer chains. This accounting is caused by the introduction of the effective kinetic energy whose density is proportional to the square of the derivative of oligomers distribution over segment numbers $`n`$. Due to the temperature dependence of the hydrogen coupling, related effective mass is a fluctuating parameter whose averaging, along the Hubbard–Stratonovich procedure, arrives at the biquadratic term with respect to the time derivative. According to the calculations given in Section IV, just this term, being considered within the mean–field approach, causes decaying character of the temperature dependence $`L(T)`$ of the structure period. Complication of the problem arising from the determination of the proper frequency $`\omega `$ is caused by an essential non–linearity and coupling the advanced/retarded Green functions and the structure factor. Hence, it is methodically convenient to use the supersymmetry technique that enables to obtain in the simplest way explicit expressions for above functions in the long–range limit (see Section III). Divergency condition of the Green function permits to find the proper frequency $`\omega `$ with accounting self–action effects within supersymmetry perturbation theory. A comparison of the dependencies obtained with experimental data given in Section V shows that the scheme developed allows to present in a self–consistent manner main peculiarities of the microphase separation in the homopolymer–oligomer systems with associative coupling.

## II Generic formalism

The problem under consideration is addressed to the definition of the effective law of motion $`c(n)`$ that determines a sequence of oligomer alternation along the homopolymer chain by means of specifying the occupation number being $`c(n)=1`$ if oligomer is attached to the segment $`n`$, and $`c(n)=0`$ otherwise. When the index of the homopolymer chain $`N\mathrm{}`$, the argument $`n`$ may be considered as a continuum one, and we are ventured to start with Euler equation 10

$$\frac{\delta S}{\delta c}\frac{\mathrm{d}}{\mathrm{d}n}\frac{\delta S}{\delta \dot{c}}=\frac{\delta R}{\delta \dot{c}}$$
(2)
where dot denotes derivative with respect to the segment number $`n`$, action $`S`$ and dissipative functional $`R`$ take the usual forms

$$S\{c(n)\}\underset{0}{\overset{N}{}}L(c(n),\dot{c}(n))dn,R=\frac{\mathrm{\Theta }}{2}\underset{0}{\overset{N}{}}\left(\dot{c}(n)\right)^2dn$$
(3)
being defined by the Lagrangian $`L(c(n),\dot{c}(n))`$ and the damping coefficient $`\mathrm{\Theta }`$, respectively. The total action $`S=K\mathrm{\Pi }`$ is determined by a ”kinetic” contribution $`K`$ of inhomogeneity in the oligomers distribution and ”potential” component $`\mathrm{\Pi }V_0+V`$ caused by the interaction between homopolymer and oligomers

$$V_0=T\frac{\tau }{2}\underset{0}{\overset{N}{}}\left(c(n)\right)^2dn$$
(4)
and self–action contribution

$$V=T\underset{0}{\overset{N}{}}v\left(c(n)\right)dn,v\frac{\mu }{3!}c^3+\frac{\lambda }{4!}c^4.$$
(5)
Here, $`T`$ is temperature measured in energy units, factor $`\tau `$ determines the strength of the hydrogen bonding, multipliers $`\mu `$, $`\lambda `$ are self–action parameters.

In comparison with the above standard approach, the determination of the contribution of inhomogeneity along polymeric chain is much more delicate problem. Indeed, the bare magnitude can be written in the form of the usual kinetic action

$$K=T\frac{m}{2}\underset{0}{\overset{N}{}}\left(\frac{\mathrm{d}c}{\mathrm{d}n}\right)^2dn$$
(6)
where an effective mass $`m`$ appears as a temperature fluctuating parameter with mean value $`\overline{m}`$ and variance $`\overline{(m\overline{m})^2}\sigma ^2`$ (bar denotes the average, as usually). Then, after averaging exponent $`\mathrm{exp}(K/T)`$ over the Gaussian distribution of the bare mass $`m`$, we obtain the effective kinetic action in the following form:

$`𝒦=\overline{K}+\stackrel{~}{K};\overline{K}T{\displaystyle \frac{\overline{m}}{2}}{\displaystyle \underset{0}{\overset{N}{}}}\left(\dot{c}(n)\right)^2dn,`$ (7)
$`\stackrel{~}{K}T{\displaystyle \frac{\sigma ^2}{8}}{\displaystyle \underset{0}{\overset{N}{}}}{\displaystyle \underset{0}{\overset{N}{}}}\left(\dot{c}(n)\right)^2\left(\dot{c}(n^{})\right)^2dndn^{}.`$ (8)
As a result, total action takes the final form

$`S=T{\displaystyle \frac{\overline{m}}{2}}{\displaystyle \underset{0}{\overset{N}{}}}\left(\dot{c}(n)\right)^2dnT{\displaystyle \frac{\sigma ^2}{8}}{\displaystyle \underset{0}{\overset{N}{}}}{\displaystyle \underset{0}{\overset{N}{}}}\left(\dot{c}(n)\right)^2\left(\dot{c}(n^{})\right)^2dndn^{}T{\displaystyle \frac{\tau }{2}}{\displaystyle \underset{0}{\overset{N}{}}}\left(c(n)\right)^2dnV`$ (9)
where self–action potential $`V`$ is given by Eqs. (5). Respectively, Euler equation (2) arrives at the equation of effective motion

$`\left(\overline{m}\stackrel{~}{\mathrm{\Delta }}\right)\ddot{c}+{\displaystyle \frac{\mathrm{\Theta }}{T}}\dot{c}+\tau c=v^{}`$ (10)
where one notices

$`v^{}T^1{\displaystyle \frac{\delta V\{c(n)\}}{\delta c(n)}}={\displaystyle \frac{v}{c}},\stackrel{~}{\mathrm{\Delta }}{\displaystyle \frac{\sigma ^2}{2}}{\displaystyle \underset{0}{\overset{N}{}}}\left(\dot{c}(n^{})\right)^2dn^{}.`$ (11)
By introducing the effective mass $`\stackrel{~}{m}`$, characteristic number of correlating segments $`n_c`$ and $`\delta `$–correlated source $`\zeta (n)`$ in accordance with definitions

$`\stackrel{~}{m}\overline{m}\stackrel{~}{\mathrm{\Delta }},n_c{\displaystyle \frac{\mathrm{\Theta }}{T}},`$ (12)
$`\zeta (n)=0,\zeta (n)\zeta (n^{})=\delta (nn^{}),`$ (13)
one obtains Langevin equation of inertial type

$$\stackrel{~}{m}\ddot{c}+n_c\dot{c}=(\tau c+v^{})+\zeta .$$
(14)
Making use of the field scheme 10  allows to express the noise $`\zeta `$ in terms of an additional degree of freedom $`p`$ being the momentum conjugated to the effective coordinate $`c`$. Following this line, one has to introduce the generating functional

$$Z\{c(n)\}\underset{n}{}\delta \left\{\stackrel{~}{m}\ddot{c}+n_c\dot{c}+\tau c+v^{}\zeta \right\}\mathrm{det}\left|\frac{\delta \zeta }{\delta c}\right|$$
(15)
being the average over the noise $`\zeta (n)`$ where $`\delta `$–function accounts for the equation of motion (14), and the determinant is Jacobian of transition from $`\zeta (n)`$ to $`c(n)`$ that is equal $`\mathrm{\Theta }/Tn_c`$. Then, making use of the functional Laplace representation of $`\delta `$–function over a ghost field $`p(n)`$ and averaging Eq.(15) over Gaussian distribution being related to Eqs.(13), we derive to the standard form 10

$`Z\{c(n)\}={\displaystyle \mathrm{exp}\left[𝒮\{c(n),p(n)\}\right]\mathrm{D}p(n)},`$ (16)
$`𝒮\{c(n),p(n)\}{\displaystyle (c(n),p(n))dn}`$ (17)
where effective Lagrangian is introduced

$$=(\stackrel{~}{m}\ddot{c}+n_c\dot{c}+\tau c+v^{})(n_c^1p)\frac{1}{2}(n_c^1p)^2.$$
(18)
According to Euler equations

$$\frac{}{x}\frac{\mathrm{d}}{\mathrm{d}n}\frac{}{\dot{x}}+\frac{\mathrm{d}^2}{\mathrm{d}n^2}\frac{}{\ddot{x}}=0,x\{c,p\}$$
(19)
effective motion in the phase space is determined by the system

$`\stackrel{~}{m}\ddot{c}+n_c\dot{c}=(\tau c+v^{})+(n_c^1p),`$ (20)
$`\stackrel{~}{m}\ddot{p}n_c\dot{p}=\left(\tau +v^{\prime \prime }\right)p.`$ (21)
A comparison of the first of these equations with Eq. (14) shows that the conjugated momentum $`p`$ appears as the most probable value of the renormalized noise amplitude $`n_c\zeta `$ 13 .

## III Supersymmetry representation of correlation in oligomer distribution

Eqs.(20), (21) represents a system of nonlinear equations whose solution demands a use of the perturbation theory with respect to the self-action parameters $`\lambda `$, $`\mu `$ and of the self–consistency procedure to determine an effective mass $`\stackrel{~}{m}\{c(n)\}`$. However, because we are interested in the knowledge not of laws of motion $`c(n)`$ and $`p(n)`$, but only of the frequency of oligomer alternation along the homopolymer chain, it is appropriate to restrict ourself to an investigation of the corresponding correlators. The latters reduce to autocorrelator $`S(n)=c^2(n)`$, and retarded and advanced Green functions, $`G_{}(n)=c(n)p(0)`$ and $`G_+(n)=p(n)c(0)`$, respectively. As shows the consideration given in 11  – 13 , it is convenient to represent these correlators as the components of the supercorrelator

$$C(z)\varphi ^2(z),z\{n,\vartheta \}$$
(22)
of pseudovectors of the phase space

$`\varphi =c+(n_c^1p)\vartheta `$ (23)
being built by making use of nilpotent variable $`\vartheta `$ which satisfies the conditions:

$`\vartheta ^2=0,\vartheta \vartheta ^{}=\vartheta ^{}\vartheta ,{\displaystyle d\vartheta }=0,{\displaystyle \vartheta d\vartheta }=1.`$ (24)
Along this line, the supercorrelator (22) appears as a pseudovector

$$𝐂=G_+𝐀+G_{}𝐁+S𝐓$$
(25)
spanned on set of the orts

$$𝐀(\vartheta ,\vartheta ^{})=\vartheta ,𝐁(\vartheta ,\vartheta ^{})=\vartheta ^{},𝐓(\vartheta ,\vartheta ^{})=1.$$
(26)
Introducing the functional product of some vectors $`X`$, $`Y`$, $`Z`$ in such a space:

$$X(\vartheta ,\vartheta ^{})=Y(\vartheta ,\vartheta ^{\prime \prime })Z(\vartheta ^{\prime \prime },\vartheta ^{})d\vartheta ^{\prime \prime },$$
(27)
it is easy to see that orts (26) are noncommutative to obey to the multiplication rules given in Table I.

As a result, making use of the supercorrelator (22) presents a big advantage in analytical calculations.

Under suppression of the inhomogeneity fluctuations along the homopolymer chain ($`\sigma =0`$), the action (17) with the Lagrangian (18) written within the harmonic approximation ($`v(c)=\mathrm{const}`$) takes the canonical form

$`𝒮_0\{\varphi (z)\}={\displaystyle \frac{1}{2}}{\displaystyle \varphi (z)L(z)\varphi (z)dz}`$ (28)
with the linear operator

$`L(z)=\tau (n)+D(z);\tau (n)\tau +\overline{m}_n^2,`$ (29)
$`_n^2={\displaystyle \frac{^2}{n^2}},D(z)={\displaystyle \frac{}{\vartheta }}+n_c\left(12\vartheta {\displaystyle \frac{}{\vartheta }}\right){\displaystyle \frac{}{n}}.`$ (30)
This operator defines the bare supercorrelator according to the relation

$$C^{(0)}(z)L^1(z)\delta (\vartheta ,\vartheta ^{}),\delta (\vartheta ,\vartheta ^{})=\vartheta +\vartheta ^{}.$$
(31)
Taking into account condition $`D^2=n_c^2_n^2`$ 11 , one obtains

$$C^{(0)}=\frac{\left[\tau (n)D\right]\delta (\vartheta ,\vartheta ^{})}{\tau ^2(n)n_c^2_n^2}.$$
(32)
Using Fourier transformation over the frequency $`\nu `$, we arrive to the expression

$`C^{(0)}={\displaystyle \frac{1+\left[\tau (\nu )\mathrm{i}n_c\nu \right]\vartheta +\left[\tau (\nu )+\mathrm{i}n_c\nu \right]\vartheta ^{}}{\tau ^2(\nu )+n_c^2\nu ^2}},\tau (\nu )\tau \overline{m}\nu ^2.`$ (33)
Then, taking into account Eqs. (25), (26), we get standard equalities for the main correlators

$$G_\pm ^{(0)}=\left[\tau (\nu )\pm \mathrm{i}n_c\nu \right]^1,S^{(0)}G_+^{(0)}G_{}^{(0)}=\left[\tau ^2(\nu )+n_c^2\nu ^2\right]^1.$$
(34)
An explicit form of linear operator

$$𝐋=L_+𝐀+L_{}𝐁+L𝐓$$
(35)
obeying to equality $`𝐋\left(𝐂^{(0)}\right)^1`$ will be needed below. Using the equality 11

$$𝐂^1=G_+^1𝐀+G_{}^1𝐁G_+^1SG_{}^1𝐓,$$
(36)
we arrive easily to the components

$$L_\pm =\tau (\nu )\pm \mathrm{i}n_c\nu ,L=1.$$
(37)
To proceed, let us consider the effective interaction term in action (9)

$$\stackrel{~}{K}T\frac{\sigma ^2}{2}\frac{\mathrm{d}\nu _1\mathrm{d}\nu _2}{(2\pi )^2}\nu _1^2\nu _2^2|c(\nu _1)|^2|c(\nu _2)|^2$$
(38)
taken in the frequency representation. Within the mean–field approximation, one has

$`|c(\nu _1)|^2|c(\nu _2)|^2|c(\nu _1)|^2|c(\nu _2)|^2+|c(\nu _1)|^2|c(\nu _2)|^2=S(\nu _1)|c(\nu _2)|^2+|c(\nu _1)|^2S(\nu _2)`$ (39)
and the fluctuational component of the inhomogeneity action (38) takes the form

$`\stackrel{~}{𝒦}\{\varphi \}=T\mathrm{\Delta }{\displaystyle \frac{\mathrm{d}\nu }{2\pi }\nu ^2|\varphi (\nu ,\vartheta )|^2\vartheta d\vartheta }`$ (40)
where parameter $`\stackrel{~}{\mathrm{\Delta }}`$ given by Eq. (11) reduces to averaged magnitude

$`\mathrm{\Delta }=\sigma ^2{\displaystyle \frac{\mathrm{d}\nu }{2\pi }\nu ^2S(\nu )}\sigma ^2{\displaystyle \frac{\mathrm{d}\nu }{2\pi }\nu ^2C(\nu ,\vartheta )\vartheta d\vartheta }.`$ (41)
As a result, the bare mass $`\overline{m}`$ in the action $`S_0`$ given by Eqs. (28), (29) is replaced by the effective quantity

$`m_{ef}\overline{m}\mathrm{\Delta }`$ (42)
being averaged value of the fluctuating mass (12).

To finish supersymmetry representation of the action (17) defined by the Lagrangian (18), one should add to Eqs.(28), (40) the self–action term

$`𝒱\{\varphi (z)\}={\displaystyle v\left(\varphi (z)\right)dz},z\{n,\vartheta \}`$ (43)
with the expansion (5). Then, the standard perturbation theory gives the symbolic expression 10

$$\begin{array}{cc}& \mathrm{\Sigma }(\vartheta _1,\vartheta _2,n)\hfill \\ & =\frac{\mu ^2}{2!}\left(C(\vartheta _1,\vartheta _2;n)\right)^2+\frac{\lambda ^2}{3!}\left(C(\vartheta _1,\vartheta _2;n)\right)^3\hfill \end{array}$$
(44)
for the self-energy function $`\mathrm{\Sigma }(\vartheta _1,\vartheta _2,n)`$ defined by the following equation for the $`n`$-point dressed supercorrelator

$$\begin{array}{cc}& C^{(n)}(\vartheta ,\vartheta ^{})\hfill \\ & =C^{(0)}(\vartheta ,\vartheta _1)\mathrm{\Sigma }^{(n)}(\vartheta _1,\vartheta _2)C^{(0)}(\vartheta _2,\vartheta ^{})d\vartheta _1d\vartheta _2.\hfill \end{array}$$
(45)
However, detailed analysis Kurchan  shows that the multiplication rules given by Table 1 has to be replaced by the rules of Table 2.

Then, the components of the pseudovector

$$𝚺=\mathrm{\Sigma }_+𝐀+\mathrm{\Sigma }_{}𝐁+\mathrm{\Sigma }𝐓$$
(46)
take the following forms:

$`\mathrm{\Sigma }(\nu )={\displaystyle \frac{\mu ^2}{2}}{\displaystyle \frac{\mathrm{d}\nu _1}{2\pi }S(\nu _1)S(\nu \nu _1)}+{\displaystyle \frac{\lambda ^2}{6}}{\displaystyle \frac{\mathrm{d}\nu _1\mathrm{d}\nu _2}{(2\pi )^2}S(\nu _1)S(\nu _2)S(\nu \nu _1\nu _2)},`$ (47)
$`\mathrm{\Sigma }_\pm (\nu )=\mu ^2{\displaystyle \frac{\mathrm{d}\nu _1}{2\pi }S(\nu _1)G_\pm (\nu \nu _1)}+{\displaystyle \frac{\lambda ^2}{2}}{\displaystyle \frac{\mathrm{d}\nu _1\mathrm{d}\nu _2}{(2\pi )^2}S(\nu _1)S(\nu _2)G_\pm (\nu \nu _1\nu _2)}.`$ (48)
Making use of the theory of residues (see Appendix B) with the correlators (34), where the frequency dependent parameter $`\tau (\nu )\tau \overline{m}\nu ^2`$ is replaced by the bare one $`\tau `$, arrives at the equalities (89), (90) which take the form

$`\mathrm{\Sigma }(8\tau ^3n_c)^1\left[\left(\mu ^2+{\displaystyle \frac{\lambda ^2}{3^2\tau n_c}}\right)\left({\displaystyle \frac{\mu ^2}{2^2}}+{\displaystyle \frac{\lambda ^2}{3^4\tau n_c}}\right)\xi ^2\right],`$ (49)
$`\mathrm{\Sigma }_\pm (4\tau ^2n_c)^1\left[\left(\mu ^2+{\displaystyle \frac{\lambda ^2}{6\tau n_c}}\right){\displaystyle \frac{\mathrm{i}}{2}}\left(\mu ^2+{\displaystyle \frac{\lambda ^2}{3^2\tau n_c}}\right)\xi \left({\displaystyle \frac{\mu ^2}{2^2}}+{\displaystyle \frac{\lambda ^2}{23^3\tau n_c}}\right)\xi ^2\right]`$ (50)
within the hydrodynamic limit $`\xi \nu /\omega _s1`$, $`\omega _s\tau /n_c`$.

Self–consistent behavior of the system under consideration is described by the generalized Dyson equation 11

$$𝐂^1=𝐋𝚺.$$
(51)
In the component representation this equality arrives at the equations

$`S=(\mathrm{\Sigma }L)G_+G_{},`$ (52)
$`G_\pm ^1=L_\pm \mathrm{\Sigma }_\pm .`$ (53)
Combination of Eqs. (37), (49), (50) arrives at the final equations for main correlators within hydrodynamical limit $`\xi 1`$:

$$\begin{array}{c}\hfill G_\pm ^1=\left[\tau (4\tau ^2n_c)^1\left(\mu ^2+\frac{\lambda ^2}{6\tau n_c}\right)\right]\\ \hfill \pm \mathrm{i}\left[\tau +(8\tau ^2n_c)^1\left(\mu ^2+\frac{\lambda ^2}{3^2\tau n_c}\right)\right]\xi \\ \hfill \left[\frac{\tau ^2m_{ef}}{n_c^2}(4\tau ^2n_c)^1\left(\frac{\mu ^2}{2^2}+\frac{\lambda ^2}{23^3\tau n_c}\right)\right]\xi ^2.\end{array}$$
(54)
## IV Determination of the period of microphase structure

Our consideration is based on the obvious equality for the long space period $`L=2l+D`$ where $`l`$ is the oligomer chain length, $`D`$ is the thickness of the homopolymer layer being fixed by the inverse share $`X^1`$ of average number of the hydrogen bonds (see Figure 1). Physically, this value is reduced to the magnitude $`2\pi /\omega `$ determined by the circular frequency $`\omega `$ in the alternation of the oligomer heads along the homopolymer chain. Then, the long space period is expressed by the following equality 2  (see Appendix A)

$$L=2l+D_0\omega ^1,D_0\left(2\pi \chi ^{1/6}n^{1/3}\right)bb$$
(55)
where $`\chi 10^1`$ is the Flory parameter, $`n10`$ is the number of segments in oligomer chain, $`b`$ is the segment length.

To obtain the frequency $`\omega `$, one has to determine firstly the effective mass $`m_{ef}`$ given by Eqs. (42), (41). Usage of the theory of residues (see Appendix B) with the structure factor (52) and Green function (54) arrives at the renormalization mass parameter

$`\mathrm{\Delta }={\displaystyle \frac{\sigma ^2}{2m_{ef}n_c}}\left(1+{\displaystyle \frac{1}{2^5}}{\displaystyle \frac{n_c\mu ^2}{\tau ^4m_{ef}}}+{\displaystyle \frac{1}{2^33^4}}{\displaystyle \frac{\lambda ^2}{\tau ^5m_{ef}}}\right)`$ (56)
where only the terms of the second order of smallness over the parameters $`\mu ,\lambda `$ of the self–action (5) are kept. Inserting here Eqs. (12), (42), we obtain the equations for determination of the effective mass as a function of the temperature:

$`m_{ef}=\mu \overline{m},\mu =\mu (T);`$ (57)
$`4\mu (1\mu )={\displaystyle \frac{T}{T_{c0}}}\left(1+{\displaystyle \frac{\alpha +\beta /T}{\mu }}\right)`$ (58)
where

$`T_{c0}\left({\displaystyle \frac{\overline{m}}{\sigma }}\right)^2{\displaystyle \frac{\mathrm{\Theta }}{2}},\alpha {\displaystyle \frac{1}{2^33^4}}{\displaystyle \frac{\lambda ^2}{\tau ^5\overline{m}}},\beta {\displaystyle \frac{1}{2^5}}{\displaystyle \frac{\mathrm{\Theta }\mu ^2}{\tau ^4\overline{m}}}.`$ (59)
Numerical solution of Eq. (58) for different values of $`\alpha `$ and $`\beta `$ allows us to estimate an influence of the self–action on the effective mass. It turned out that even small variation of the parameter $`\alpha `$ substantially changes the shape of the dependence $`\mu (T)`$, whereas the parameter $`\beta `$ almost does not affect it, and we can put $`\beta =0`$ for the sake of simplicity. This means physically that the cubic anharmonicity in the self–action potential energy (5) is irrelevant to the microphase separation phenomenon.

The smallness of the self–action parameters $`\alpha `$, $`\beta `$ allows us to solve Eq. (58) analytically. In so doing, one has to replace the required dependence $`\mu (T)`$ in the right hand part of Eq. (58) by the bare dependence

$`\mu _0(T)={\displaystyle \frac{1}{2}}\left(1+\sqrt{1{\displaystyle \frac{T}{T_{c0}}}}\right),`$ (60)
that is a solution of this equation at $`\alpha =\beta =0`$. As a result, we obtain the simple dependence

$`\mu (T)={\displaystyle \frac{1}{2}}\left(1+\sqrt{1{\displaystyle \frac{T}{T_c}}}\right)`$ (61)
with a characteristic temperature

$`T_cT_{c0}\left(12\alpha \right)`$ (62)
where the scale $`T_{c0}`$ is given by the first of Eqs. (59) (the multiplier should be put $`\mu _0(T_{c0})1/2`$ due to the smallness of the parameter $`\alpha 1`$). According to Eq. (61), with the temperature increasing the effective mass (57) decreases monotonously from the bare magnitude $`\overline{m}`$ at $`T=0`$ to $`\overline{m}/2`$ at $`T=T_c`$ (see the main panel in Figure 2). The critical temperature $`T_c`$ determines the point of the order-disorder transition according to the condition

$$\frac{\mathrm{d}\mu }{\mathrm{d}T}=\mathrm{}.$$

Resulting dependence $`T_c`$ on the self–action parameter $`\alpha `$ is shown in the inset of Figure 2. It is principally important that the bigger value of the self–action parameter $`\alpha `$, the more narrow is the temperature domain $`T_g÷T_c`$ where the microphase separated structure is possible ($`T_g`$ being a glassing temperature). In other words, the self–action effect leads to the shrinking the region of the ordered structure because the critical temperature $`T_c`$ reaches the boundary magnitude $`T_g`$ with increasing of $`\alpha `$ before the magnitude $`\alpha 0.08`$.

The divergency condition $`G_{}^1=0`$ of the Green function (54) gives the proper frequency

$`\nu _0=\pm \omega \mathrm{i}\varpi ,\omega \sqrt{\omega _0^2\varpi ^2}`$ (63)
of the oligomer alternation along the homopolymer chain. Real and imaginary parts are determined by the expressions

$$\begin{array}{c}\hfill \omega _0\frac{\overline{\omega }_0}{\sqrt{\mu (T)}}\left[1+3\alpha \left(1\frac{9}{8}\frac{T^2}{T_0^2}\right)\right],\\ \hfill \varpi \frac{\overline{\omega }_0}{\mu (T)}\frac{T_0}{T}\left[1+6\alpha \left(1+\frac{3}{8}\frac{T^2}{T_0^2}\right)\right]\end{array}$$
(64)
where the dependence $`\mu (T)`$ is defined by Eqs. (61), (62); the effective mass in parenthesis after the factor $`\alpha 1`$ is put to be equal to the value $`\overline{m}/2`$ related to the critical temperature $`T_c`$; characteristic scales of both frequency and temperature are introduced as follows:

$$\overline{\omega }_0\sqrt{\frac{\tau }{\overline{m}}},T_0\frac{\mathrm{\Theta }}{2\sqrt{\overline{m}\tau }}.$$
(65)
As a result, combination of Eqs.(55), (63) and (64) leads to the final result for the long space period

$$L=2l+\frac{\mu (T)}{\sqrt{\mu (T)(T_0/T)^2}}\left[1+\frac{3}{2}\alpha \frac{1+8(T_0/T)^2+\frac{9}{4}(T_0/T)^2}{12(T_0/T)^2}\right]L_0$$
(66)
where the characteristic length $`L_0D_0/\overline{\omega }_0\sqrt{\overline{m}/\tau }\chi ^{1/6}b\chi ^{1/6}N^{1/2}`$ is the function of both parameters $`\chi `$ and $`N`$ being thermodynamically independent. Thus, the first of the exponents in the scaling relation $`L_0\chi ^aN^b`$ takes the magnitude $`a=1/6`$ inherent to the strong segregation regime, whereas the second one ($`b=1/2`$) is the same for the weak one a . Note that the obtained $`\chi `$–dependence is caused by the multiplier $`\chi ^{1/6}`$ in the generic relation (55) that is relevant to the former of above regimes, while the method developed addresses to the latter.

## V Discussions

The behavior of the system under consideration is controlled by the parameters $`\overline{m}`$, $`\tau `$ and $`\sigma `$ which determine the temperature $`T_c`$ of the order–disorder transition and the long space period $`L`$ given by Eqs. (62), (66), respectively. Moreover, there is the self–action parameter $`0<\alpha 1`$ whose value is limited by the magnitude $`\alpha _{max}0.08`$ (see insert in Figure 2). To guarantee positive values of the radicand in Eq. (66) at the critical temperature $`T_c`$, the above parameters have to be constrained by the condition

$$\kappa \sqrt{2}$$
(67)
limiting magnitudes of the principal parameter

$$\kappa \frac{T_c}{T_0}=\sqrt{\tau \overline{m}}\left(\frac{\overline{m}}{\sigma }\right)^2(12\alpha ).$$
(68)
The minimal magnitude of $`\kappa `$ fixes the choice of the theory parameters according to the condition

$$\sigma 2^{1/4}\overline{m}^{5/4}\tau ^{1/4}(1\alpha ).$$
(69)
It would seem from Eqs. (67), (68) that the decrease of the critical temperature $`T_c`$ with passing from the ionically bonded system (such as P4VP–(DBSA)x) to the hydrogen bonded one (e.g., P4VP–(PDP)x) is caused only by the growth of the fluctuation parameter $`\sigma `$ with respect to the mean magnitude of the inhomogeneity parameter $`\overline{m}`$. It appears, however, that the main reason for such behavior is given by the decrease of the mean–geometrical magnitude $`\sqrt{\overline{m}\tau }`$ of the principal coefficients in the generic Lagrangian (9) (see below).

To clarify this problem and find explicit form of the dependencies of the temperature of order-disorder transition $`T_c`$ and the period $`L`$ on the oligomeric fraction $`x`$, we assume for main theory parameters $`\overline{m}`$ and $`\tau `$ the three–parametric relations:

$$\overline{m}=m_0+Ax(x_mx),\tau =\tau _0+Bx(x_\tau x)$$
(70)
with positive constants $`m_0`$, $`\tau _0`$, $`A`$, $`B`$, $`x_m`$, $`x_\tau `$ to be determined. Then, the fitting of the experimental results shown in the Figure 3 in accordance with Eq. (66) where $`\tau `$, $`\overline{m}`$ are given by Eq. (70) leads to the following results for the ionically bonded systems:

* the mixtures P4VP–(DBSA)$`_x`$

$$\begin{array}{cc}& m_0=18,A=8,x_m=1.5;\hfill \\ & \tau _0=0.6,B=1.5,x_\tau =1.0;\hfill \\ & \alpha =0.01;b=1nm;l=10nm;\hfill \end{array}$$
(71)
* the mixtures P4VP–(Zn(DBS)2)$`_x`$

$$\begin{array}{cc}& m_0=5.3,A=26,x_m=1.6;\hfill \\ & \tau _0=0.8,B=0.1,x_\tau =1.0;\hfill \\ & \alpha =0.01;b=1nm;l=10nm.\hfill \end{array}$$
(72)

At $`x=1`$ one obtains $`\overline{m}=22`$, $`\tau =0.6`$ for P4VP–(DBSA)x and $`\overline{m}=20.9`$, $`\tau =0.8`$ for P4VP–(Zn(DBS)2)x. Then, Eq. (68) gives values $`\kappa =10^3`$, $`10^2`$ at $`\sigma =1.31`$, $`4.18`$, respectively.

Much more complicated situation occurs in the weakly bonded system P4VP–(PDP)x. Here, decrease of the parameter (68) results in the narrowing of the temperature domain $`T_0÷T_c`$ of the phase separation. All parameters for this class of systems can be determined by the combined fitting of a series of experimental data for the critical temperature $`T_c`$ and the long space period $`L`$ (see Figures 46). First constraints follow from the comparison of experimental points for the temperature $`T_c`$ of order–disorder transition (see Figure 4) with fitting results based on Eq. (62) at $`\alpha =0.01`$, $`l=10`$ nm:

$$\frac{\mathrm{\Theta }m_0^2}{\sigma ^2}=562,\frac{A}{m_0}=0.155,x_m=1.615.$$
(73)
The following of parameters gives application of Eq. (66) for the long space period at the temperature $`T=T_c`$ to the data shown in Figure 5 as the non-monotonous curve:

$$\frac{m_0}{\tau _0}=1499,\frac{B}{\tau _0}=7.968,x_\tau =1.926.$$
(74)
Finally, making use of the expression (66) and experimental data for the temperature dependence of the long space period given in Figure 6 yields the last constraint

$$\frac{\mathrm{\Theta }}{\sqrt{m_0\tau _0}}=924.$$
(75)
As a result, taking $`m_0=1`$ at $`x=1`$ the magnitudes $`A=0.155`$, $`\mathrm{\Theta }=23.87`$, $`\sigma =0.206`$ are obtained to provide extremely small value $`\tau =5.610^3`$ of the hydrogen bonding strength and the temperature scale $`T_0=160`$. At $`\alpha =0.01`$ this arrives to the rest of parameters $`\kappa =2.07`$, $`\lambda =6.2210^6`$.

It is worthwhile to discuss separately the dependence of the long space period on the oligomer/monomer ratio at the temperature $`T=80^0\mathrm{C}`$ that relates to the monotonous decaying curve shown in Figure 5. Because the maximal temperature of the order–disorder transition is $`T_c65^0\mathrm{C}`$ to be corresponded to $`x=0.85`$ (see Figure 4), experimental data related to $`T=80^0\mathrm{C}`$ are obtained for the temperature being beyond of the region of the ordered structure ($`T>T_c`$). From the physical point of view, at the critical temperature $`T=T_c`$ the periodicity of the microphase separated structure formed is caused by long–range correlations, whereas at $`T=80^0\mathrm{C}`$ only short–range correlations hold to be determined by the homopolymer backbone together with the hydrogen bound surfactant molecules 8 . Fitting of the experimental points for the dependence $`L(x)`$ at the temperature $`T=80^0\mathrm{C}`$ can be done on the base of Eq. (66) where one puts $`\mu (T)=\mu (T_c)=1/2`$. Then, the values of the parameters obtained differ from those obtained for $`T=T_c`$ by the following constraints:

$$\frac{B}{\tau _0}=4.2,x_\tau =3.27,\frac{\mathrm{\Theta }}{\sqrt{m_0\tau _0}}=543.$$
(76)
Obviously, this difference is due to the temperature dependence of the hydrogen bonding parameter $`\tau `$ in the potential energy (4).

To conclude our estimations, we notice the model developed explains successfully a vast variety of peculiarities obtained experimentally for various classes of homopolymer–oligomer mixtures with the interactions of different strength. The resulted data for strong, intermediate and weak coupled systems P4VP–(DBSA)x, P4VP-(Zn(DBS)2)x and P4VP–(PDP)x, respectively, are given in Table III.

It is seen that the coupling weakening arrives to a decrease of both inhomogeneity parameters $`\overline{m}`$ and $`\sigma `$, as well as to the crucial decrease of the hydrogen bonding parameter $`\tau `$ and the self–action parameter $`\lambda `$, on the one hand, and the characteristic temperatures $`T_c`$ and $`\mathrm{\Theta }`$, on the other hand. According to the relations (68) this leads to extremely large suppression of the value of the parameter $`\kappa `$ that causes the crucial shrinking the temperature interval of the microphase separation. An analogous effect is caused by the self–action increase.

To get rid of a misunderstanding, we would like to stress a composite character of the approach used. As it is mentioned in Introduction, this circumstance is expressed by dividing the total free energy (1) into two terms, the first one $`F_{ho}`$ is relevant to the non–associated homopolymer–oligomer mixture, the second one $`F_{hb}`$ is caused by the hydrogen bonding. These terms are caused by the interactions of principally different physical nature: the behavior of the mixture of non–associated homopolymers and oligomers is determined by the Flory parameter $`\chi `$, characterizing unfavorable interactions between the the oligomers and the rest of the system; the temperature induced distribution of hydrogen bonds is determined by the parameter $`\tau `$, giving the strength of this bonding. From the formal point of view, both of the above contributions $`F_{ho}(\chi ,\varphi )`$ and $`F_{hb}(\tau ,x)`$ should have a similar dependencies on the state parameters being (apart from the temperature) the volume fraction of the homopolymer $`\varphi `$ for the first contribution, and the oligomer/monomer ratio $`x`$ for the second one. Because the term $`F_{ho}\chi \varphi (1\varphi )`$ involves the parabolic dependence on the parameter $`\varphi `$ bounded by maximal value $`\varphi =1`$, we took generalized parabolic approximation (70) for the dependence of the hydrogen bonding strength $`\tau `$ on the oligomer/monomer ratio $`x`$ which may take values $`x>1`$.

Apart from the above difference in nature of the interactions, one needs to emphasize at once the difference in the approaches used: the mixture of non–associated homopolymers and oligomers had been studied within the strong segregation limit 2 , whereas for the consideration of the hydrogen bonding we use opposite approach. This difference is kept if the Flory parameter takes large values $`\chi 10^1`$, whereas the hydrogen bonding strength is relatively small ($`\tau 1`$). Indeed, the formula (55) for the long space period was obtained within approximation of the sharp interface, which thickness is $`\mathrm{\Delta }\chi ^{1/2}b3b`$ to be relevant to the strong segregation regime 2 . In the consideration presented, we have focused mainly on the study of the hydrogen bonding on the base of the action (9) that has the form of series in powers of the order parameter $`c`$ and its derivatives $`\dot{c}`$. Such an expansion supposes making use of the weak segregation limit corresponding to the small values of the parameters $`\overline{m}`$ and $`\tau `$.

Finally, it is worthwhile to discuss a difference with an usual picture of the phase transitions that is caused by the self–consistency condition (41). A critical value of the Flory parameter $`\chi _c`$ in usual copolymers is known to be caused by the self–action effects. The accounting of these effects arrives to replacement the bare parameter $`\chi `$ by the renormalized value $`\chi \chi _c`$ 19 . However, in our case the value of Flory parameter is so large that the temperature of the separation of non–associated polymer–oligomer mixture is negligible small. As a result, the role of $`\chi `$ passes to the hydrogen bonding parameter $`\tau `$ which does not relate to the tendency of monomers of the different kinds to avoid each other. However, as it is shown by the considerations given in 26 , 27 , understanding of the whole picture of microphase separation, including the temperature dependence of the structure period, demands accounting the inhomogeneity in the distribution of oligomers along homopolymer chains. Within the approach developed, this is reached by means of the effective kinetic energy (6), with the mass fluctuating due to the temperature dependence of hydrogen bonding. This dependence leads to the reduction (42) of the effective mass $`m_{ef}`$ that causes a phase transition from stochastic to periodic distribution of the oligomers along the homopolymer chain. However, if the critical point is fixed usually by the condition $`m_{ef}=0`$ 10 , in our case the critical temperature $`T_c`$ relates to the finite magnitude $`m_{ef}=\overline{m}/2`$ of the effective mass which has a singularity $`\mathrm{d}m_{ef}/\mathrm{d}T=\mathrm{}`$ in the temperature derivative (see Figure 2).

###### Acknowledgements.

In this work, financial support by the Grant Agency of the Czech Republic (grant GAČR 203/02/0653) is gratefully acknowledged.

## Appendix A Derivation of a generic relation for microphase structure period

Following 2  we suppose the period of the microphase structure to be determined by the minimum of the specific free energy

$$f\frac{1}{V}\frac{F_{int}+F_{str}}{T};VLS,L2l+D$$
(77)
related to the first term in Eq. (1). Being the free energy of the homopolymer–oligomer mixture, this term consists of the interfacial and stretching components $`F_{int}`$, $`F_{str}`$ measured in the temperature units $`T`$ per the domain volume $`V`$ (according to Figure 1 $`L`$, $`l`$ and $`D`$ are the long space period, the length of the oligomer tail and the thickness of the homopolymer layer, respectively; $`S`$ is the domain surface area).

The interfacial free energy is stipulated by the loss of conformational entropy caused by the localization of the homopolymer chains within the interface of thickness $`\mathrm{\Delta }`$. Due to unfavorable interaction $`\chi `$ between the oligomer tails and the polymer layer the chains form up loops containing segments of number $`𝒩_s\chi ^1`$ Helfand1971 . Then, within the model of the random walk, the interface thickness is estimated by the relations $`\mathrm{\Delta }^2𝒩_sb^2b^2/\chi `$ where $`b`$ is the segment length. Respectively, the interfacial free energy $`F_{int}𝒩_lT`$ is determined by the number $`𝒩_lS\mathrm{\Delta }/𝒩_sb^3`$ of the loops within the interface. As a result, we obtain the estimation

$$F_{int}\frac{\chi ^{1/2}}{b^2}TS.$$
(78)
Another addition $`F_{str}`$ is caused by the stretching of the surfactant side chains, whereas the stretching of the homopolymer chains enlarges only the volume part of the free energy. This addition is expressed by the simple equality $`F_{str}𝒩_cn_sF_1`$ where the first factor $`𝒩_cDS/Nb^3`$ gives the number of chains per layer, the second multiplier $`n_s(b/\lambda )N`$ is the number of the oligomer molecules per chain of $`N`$ segments ($`\lambda `$ is period of the oligomers alternating along the chain) and the last factor $`F_1(l^2/nb^2)T`$ presents the free energy of stretching a side chain of $`n`$ segments to a length $`l`$. Combining the above multipliers, we find the estimation for the total free energy of stretching

$$F_{str}\frac{l^2DS}{nb^4\lambda }T.$$
(79)
To derive the explicit expression for the dependence of the free energy (77) on the layer thickness $`D`$ we need to use an obvious condition $`2lS𝒩_cn_sv_s`$ where $`v_s=nb^3`$ is the volume of surfactant molecule. As a result, we obtain the relation

$$\frac{2l}{D}\frac{b}{\lambda }n,$$
(80)
according to which the period $`\lambda `$ defines the rest of geometrical characteristics of the microphase separated structure. Inserting Eqs. (78) — (80) into Eq. (77), we arrive to the final expression for the interfacial free energy:

$$f\frac{\frac{\chi ^{1/2}}{D}+\frac{n}{\lambda ^3}D^2}{\left[1+(b/\lambda )n\right]b^2}$$
(81)
where numerical coefficients are dropped. The minimization condition $`f/D=0`$ arrives at the steady–state values of the homopolymer layer thickness and the oligomer length

$$D\frac{\chi ^{1/6}}{n^{1/3}}\lambda ,2l\left(\chi ^{1/6}n^{2/3}\right)b.$$
(82)
It is convenient to express above results by means of the dimensionless frequency of the oligomer alternating along the homopolymer chain:

$$\omega \frac{2\pi }{\lambda /b}=\omega _{max}X;\omega _{max}2\pi ,X\frac{b}{\lambda }$$
(83)
where $`X`$ is the averaged oligomeric fraction per homopolymer. So, the long space period of the microphase separated structure takes the form

$$L2l+D\chi ^{1/6}n^{1/3}\left(n+\frac{2\pi }{\omega }\right)b.$$
(84)
## Appendix B Calculations of convolution integrals

### Self–energy functions

Calculations of the self–energy functions (47), (48) lead to a rather tedious procedure due to the convolution integrals. To demonstrate the line of these calculations we consider in details the simplest integral related to the first term in Eq. (48):

$`\mathrm{\Sigma }_{}^\mu (\nu )=\mu ^2{\displaystyle \frac{\mathrm{d}\nu _1}{2\pi }S(\nu _1)G_{}(\nu \nu _1)}.`$ (85)
Making use of the expressions (34) for the structure factor $`S`$ and Green function $`G_{}`$, where the frequency dispersed parameter $`\tau (\nu )`$ is replaced by its bare magnitude $`\tau `$, arrives at the convolution integral

$`\mathrm{\Sigma }_{}^\mu (\nu )={\displaystyle \frac{\mu ^2}{2\pi n_c^3}}{\displaystyle \frac{\mathrm{d}\nu _1}{(\omega _s^2+\nu _1^2)\left[\omega _s\mathrm{i}(\nu \nu _1)\right]}}`$ (86)
where a characteristic frequency $`\omega _s\tau /n_c`$ is introduced. This integral has the poles $`\pm \mathrm{i}\omega _s`$ and $`\nu +\mathrm{i}\omega _s`$ (see Figure 7a).

In accordance with the theory of residues book poles , the integral in Eq. (86) is reduced to sum over two of these residues that locate in upper half–plane of the complex frequency $`\nu _1`$:

$$2\pi \mathrm{i}\left[\frac{\mathrm{i}}{2\mathrm{i}\omega _s(\nu )}+\frac{\mathrm{i}}{\nu (\nu +2\mathrm{i}\omega _s)}\right]$$
(87)
where terms in the square brackets relate to the poles $`\mathrm{i}\omega _s`$ and $`\nu +\mathrm{i}\omega _s`$, respectively. After a simple algebra this expression yields

$`\mathrm{\Sigma }_{}^\mu ={\displaystyle \frac{\mu ^2}{\tau ^2n_c}}{\displaystyle \frac{1+\frac{\mathrm{i}}{2}\xi }{4+\xi ^2}},\xi {\displaystyle \frac{\nu }{\omega _s}}.`$ (88)
Analogously, the rest of convolution integrals is calculated giving final form of Eqs.(47), (48):

$`\mathrm{\Sigma }={\displaystyle \frac{\mu ^2}{2\tau ^3n_c}}{\displaystyle \frac{1}{4+\xi ^2}}+{\displaystyle \frac{\lambda ^2}{8\tau ^4n_c^2}}{\displaystyle \frac{1}{9+\xi ^2}},`$ (89)
$`\mathrm{\Sigma }_\pm ={\displaystyle \frac{\mu ^2}{\tau ^2n_c}}{\displaystyle \frac{1\frac{\mathrm{i}}{2}\xi }{4+\xi ^2}}+{\displaystyle \frac{\lambda ^2}{8\tau ^3n_c^2}}{\displaystyle \frac{3\mathrm{i}\xi }{9+\xi ^2}}.`$ (90)
### Renormalization mass parameter

Explicit form of the renormalization mass parameter (41) is determined by the structure factor (52) and Green function (54) with the effective mass (42) and parameter $`\tau (\nu )`$ being replaced by bare $`\tau `$:

$$\mathrm{\Delta }=\frac{\sigma ^2}{\pi n_cm_{ef}}\frac{(\xi _1\xi _0^1\xi ^2)\xi ^2\mathrm{d}\xi }{(\xi ^22\mathrm{i}\xi _1\xi \xi _2^2)(\xi ^2+2\mathrm{i}\xi _1\xi \xi _2^2)}$$
(91)
where one denotes

$$\begin{array}{cc}\hfill \xi _0& \frac{16m_{ef}\tau }{n_c}\left(\frac{\mu ^2}{4}+\frac{\lambda ^2}{3^4\tau n_c}\right)^1,\hfill \\ \hfill \xi _1& \frac{n_c^2}{2m_{ef}\tau }\left[1+\frac{1}{8\tau ^3n_c}\left(\mu ^2+\frac{\lambda ^2}{9\tau n_c}\right)\right],\hfill \\ \hfill \xi _2^2& \frac{n_c^2}{m_{ef}\tau }\left[1\frac{1}{4\tau ^3n_c}\left(\mu ^2+\frac{\lambda ^2}{6\tau n_c}\right)\right].\hfill \end{array}$$
(92)
The integral in Eq. (91) has the pole structure that is shown in Figure 7b. As above, the sum over residues located in the upper half–plane of the complex frequency $`\xi `$ yields the integral value

$$\frac{\pi }{2}\left(1\frac{\xi _2^24\xi _1^2}{\xi _0\xi _1}\right).$$
(93)
With accounting the notices (92) and keeping only the terms of the second order of smallness over parameters $`\mu `$ and $`\lambda `$, one obtains the final expression (56).


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# Application of Bryan’s algorithm to the mobility spectrum analysis of semiconductor devices

## I Introduction

The characterization of semiconductor devices is essential for the development of new materials which are interesting from both a physical and technological point of view. Hall-effect measurements are very frequently used for this characterization, especially when two-dimensional systems are investigated.Stradling and Klipstein (1990)

The simplest ideal material has a single charge carrier with isotropic energy bands and energy-independent scattering mechanisms. The resulting longitudinal resistivity $`\rho `$ and Hall coefficient $`R_H`$ are constant with respect to the application of magnetic field. Such a picture is effective in a basic understanding of certain solid state phenomena.

In modern semiconductor devices, heterostructures are increasingly employed where different semiconductor materials are grown epitaxially in layers on a substrate. In this manner, structures can be designed in which charge carriers are confined in a quantum well physically remote from the dopant atoms they originate from; ionized impurity atoms can strongly limit the mobility of charge carriers so this method of *modulation doping* can lead to greatly enhanced transport properties.Schäffler (1997); von Känel et al. (2002); Myronov et al. (2002)

However, the physics of magnetotransport in such heterostructures is considerably more complicated if there are two or more distinct carrier gases present in the material (for example, the intended carrier gas in the quantum well plus the doped region) or the carrier gases feature a spread of mobilities due to energy-dependent scattering mechanisms or multiple subband occupancy. This leads to resistivities and Hall coefficients which are dependent on the applied magnetic field, and to extract the properties of such systems the simple single-carrier model is not sufficient. To this end, various mobility spectrum techniques have been employed.Koschinski et al. (1995); Dziuba et al. (1997); von Känel et al. (2002); Myronov et al. (2002)

In a seminal paper, based on the work of McClure,McClure (1956) Beck and AndersonBeck and Anderson (1987) showed that the conductivity tensor depends on a generalized conductivity function, $`s(\mu )`$, via the integral transforms,

$$\sigma _{XX}(B)=_{\mathrm{}}^{\mathrm{}}\frac{s(\mu )}{1+\mu ^2B^2}𝑑\mu $$
(1)
and

$$\sigma _{XY}(B)=_{\mathrm{}}^{\mathrm{}}\frac{\mu Bs(\mu )}{1+\mu ^2B^2}𝑑\mu $$
(2)
where

$$s(\mu )=n_s(\mu )e\mu $$
(3)
and $`n_s(\mu )`$ represents the number (per unit area) of carriers with a mobility $`\mu `$ averaged over the sample.

The Hall coefficient and resistivity are related to the elements of the conductivity tensor in the standard way,

$$\rho (B)=\rho _{XX}=\frac{\sigma _{XX}}{\sigma _{XX}^2+\sigma _{XY}^2}$$
(4)
$$R_H(B)=\frac{\rho _{XY}}{B}=\frac{1}{B}\frac{\sigma _{XY}}{\sigma _{XX}^2+\sigma _{XY}^2}$$
(5)
The function $`s(\mu )`$ appearing in Eqs. (1)-(3) is often known as the mobility spectrum. It gives the contribution to the conductivity due to the density of carriers with mobility $`\mu `$. In this investigation, it is assumed that $`s(\mu )`$ does not change with magnetic field. At high fields and low temperatures this is not true because of the formation of Landau levels: the density of states becomes a function of magnetic field if $`\mathrm{}\omega _c>k_BT`$ where $`\omega _c`$ is the cyclotron frequency $`eB/m^{}`$.Coleridge et al. (1989) Also, at very low fields and low temperatures (such that $`\mu B<\mathrm{}/E_F\tau `$ where $`E_F`$ is the Fermi energy and $`\tau `$ is the momentum relaxation time) quantum effects such as weak localization contribute to the magnetoresistance.Kearney (1992)

According to Eqns. (1) and (2) magnetoresistance is always positive; negative magnetoresistance can only be analyzed by assuming a magnetic-field dependent mobility or momentum relaxation time.Dziuba et al. (1999); Dmitriev et al. (2001)

Finding the magnetoresistance given a form for the mobility spectrum is straightforward. However, performing the so-called inverse transform problem (that is, finding the mobility spectrum from magnetoresistance data) is non-trivial with a noisy, limited data set and is the subject of much investigation.Beck and Anderson (1987); Kim et al. (1993); Kim (1999); Regiński et al. (1997); Meyer et al. (1997); Vurgaftman et al. (1998); Kiatgamolchai (2000); Kiatgamolchai et al. (2002)

We replace the traditional MAXENT algorithm used by Kiatgamolchai *et al.* Kiatgamolchai (2000); Kiatgamolchai et al. (2002) with Bryan’s algorithm.Jarrell and Gubernatis (1996) This approach has two major advantages over the previous technique: (1) A Bayesian analysis is performed on the resulting spectrum, and (2) the search process is optimized by null space decomposition of the kernel. The Bayesian aspect of Bryan’s algorithm ensures that we choose the most probable balance between the fit quality, given by least squared minimization, and the information content of the solution, given by the maximization of entropy. The null space decomposition provides an exponential basis for the solution. The exponential basis is particularly well suited to this type of problem since it significantly reduces the number of dimensions in the search space. It therefore allows reliable well-conditioned analysis of greater quantities of data, avoiding the need for potentially biased data selection. In this way, the results should be relatively free from common artifacts such as mirror peaks, peaks of unnatural shape, or structure in the spectrum at very low mobility values, provided that the artifacts are not introduced by systematic measurement errors.Achard et al. (2000)

We present this paper as follows. In Sec. II, early approaches to this problem are reviewed, before considering the method of maximum entropy in more detail. In Sec. III, the maximum entropy method used in this paper is introduced, and technical details of Bryan’s algorithm are described. In Sec. IV, we perform a case study on model data using our Bryan’s Algorithm Mobility Spectrum (BAMS) method. The usefulness of the mobility spectrum technique for the analysis of real data is discussed in light of these results, and a brief summary is given in Sec. V.

## II Background

The approach of Beck and Anderson,Beck and Anderson (1987) which first introduced the concept of the mobility spectrum and has been developed into commercial software, involves a multi-stage solution method (the numerical details of which will not be explored). The number of data points used to create a solution is equal to the number of distinct carriers gases within the sample, plus one. The method either searches for an imposed number of carrier gases or fits for a single carrier system, then a two-carrier system, and so on. During each search for $`n`$ gases, the method tries fitting to every available combination of $`n+1`$ data points from the complete data set, only keeping the sets which lead to “physical” solutions. From the retained sets, the algorithm generates an “envelope function” within which the mobility spectrum should be contained.

Once a set of carrier gases has been found, the validity of the solution is confirmed by performing a least-squares fit on the original data with respect to the carrier gas parameters. If the parameters emerge virtually unchanged from the second stage, then the results of the original analysis are considered to be reasonable.

If only a limited number of data points ($`10`$) are available and the system contains only two or three distinct (i.e. with mobilities which differ significantly from each other) carrier gases, then this method is quite efficient. However, with automated systems the data collected can comprise thousands of values and the system simply cannot cope; choosing points or creating averaged data by hand imposes artificial constraints on the final solution. Also, this method does not respond well to errors in the experimental data.Kiatgamolchai (2000)

Reference Kim et al., 1993 introduces and describes the Reduced Conductivity Tensor method for extracting the carrier concentration and mobility of each component of a multilayer semiconductor system. It is assumed that the carrier gases are essentially degenerate and that the effective mass is isotropic. These assumptions immediately remove the possibility of gaining insight into energy-dependent scattering mechanisms in non-degenerate systems, and also the possibility of analyzing for example *p*-type conduction in pure germanium in which the anisotropy of the heavy hole band should be evident as “harmonics” in the mobility spectrum.Goldberg et al. (1957); McClure (1956); Beer and Willardson (1958) Nevertheless, the method works well for up to three carrier gases.

In Ref. Regiński et al., 1997 it is assumed that the mobility for a gas subjected to mixed scattering can be approximated by the phenomenological expression:

$$\mu =\mu _0x^\alpha \text{ where }x=\frac{E}{k_BT}$$
(6)
and that the mobility spectrum of non-degenerate carriers in a spherical band can be approximated by:

$$s(\mu )=S_0e^{x(\mu )}x(\mu )$$
(7)
where $`S_0`$, $`\mu _0`$ and $`\alpha `$ are coefficients depending on the density of states and on the parameters of the scattering mechanisms. Then, the integrations in Eqs. (1) and (2) are converted to summations of discrete spectra for electrons and holes and an iterative transformation procedure may be performed. The results are decomposed into high and low-mobility carrier contributions. The distinction between low-mobility carriers and high-mobility carriers is to some extent arbitrary, however, it corresponds to the visible separation between two different regions on the mobility spectrum. Results for the high-mobility carrier gas seem much more satisfactory than results for the low-mobility carrier gas in each case.

References Meyer et al., 1997 and Vurgaftman et al., 1998 describe the *quantitative mobility spectrum technique* (QMSA) and the *improved quantitative mobility spectrum technique* (i-QMSA) respectively. These are also iterative techniques but with no initial assumption about the solution (although the Beck-AndersonBeck and Anderson (1987) approach is used to create a trial solution, and conductivity data is extrapolated to higher magnetic field values to extend the available mobility range). The i-QMSA method introduces a few extra tricks for improving the fits whilst smoothing the spectra and making them more physically reasonable. This method has also been successfully applied to conduction in anisotropic bands by incorporating an explicit anisotropy coefficient.Vurgaftman et al. (1999) In Ref. Kiatgamolchai et al., 2002 it is shown that this method does not deal with error very well.

## III Maximum Entropy

A serious issue (regarding inverse transformation problems in general) is that while a particular spectrum $`s(\mu )`$ may easily be transformed to produce a magnetoconductivity $`\sigma (B)`$, the inverse problem is ill-conditioned and the solution obtained for $`s(\mu )`$ by inverting the kernel is extremely sensitive to small changes or errors in the $`\sigma (B)`$ data. In particular, there is not necessarily a unique $`s(\mu )`$ within the uncertainty bounds of the original data. For example, since the integral transform has a blurring effect, then it is possible for the data to have large local fluctuations while producing a smooth $`\sigma (B)`$.

The technique of *Maximum Entropy* has been employed to solve this and other problems involving inverse integral transformation where the result is a positive, additive function.Kiatgamolchai et al. (2002); Sivia (1990); Jarrell and Gubernatis (1996); Chrastina (2001); Chu and Dowsett (1997) Generally, if two solutions (found by any means) are of equal merit (in terms of, for example, their least-squares fits to the original results) then the solution with the larger “entropy” is to be favoured, since it is maximally non-committal with regard to missing (unmeasured) information in the original data.Kiatgamolchai et al. (2002); Jaynes (1957) In other words, the solution favoured by the maximum entropy method extracts the most information out of the original data with the most reasonable assumptions regarding information which is unavailable.

By discretising the mobility spectrum $`\{s\}`$, the entropy $`S`$ can be defined as:Gubernatis et al. (1991)

$$S\{s_j\}=\underset{j=1}{\overset{N}{}}(p_jm_jp_j\mathrm{ln}p_j/m_j)$$
(8)
$$p_j=\frac{s_j}{\sigma _0}$$
(9)
where $`p_j`$ is chosen so that the spectrum has a normalization of unity and $`\sigma _0`$ is the conductivity at zero magnetic field. The form of the entropy imposes the condition that the mobility spectrum is non-negative, which is physically realistic. If any prior information about the form of the spectrum is available then this may be incorporated as a so-called *default model* $`\{m\}`$.Jarrell and Gubernatis (1996)

Fitting is now a matter of minimizing the function $`Q`$:Jarrell and Gubernatis (1996)

$$Q=\chi ^2\alpha S$$
(10)
where $`\chi ^2=\frac{1}{2}_i\left(\frac{\sigma (B_i)\sigma _c(B_i)}{\delta _i}\right)^2`$; $`\sigma _c(B)`$ is magnetoconductivity calculated from the fitting mobility spectrum, $`\delta `$ is the error in the data such that a chi-squared which respects the data has a value of approximately $`M`$ (the number of “observations” or data points) and $`\alpha `$ is a hyper-parameter which controls the relative importance of the least-squares and entropic constraints.Jarrell and Gubernatis (1996)

There are various flavors of the maximum entropy method, which differ in the way $`\alpha `$ is determined. In the case of historic maximum entropy, different values of $`\alpha `$ are tried, until the minimization of $`Q`$ \[Eq. (10)\] gives $`\chi ^2=M`$. In the case of classic maximum entropy, the most probable value of $`\alpha `$ is found, given the data and the default model.Gubernatis et al. (1991); Gallicchio and Berne (1996) Alternatively, the method described in Ref. Jaynes, 1957 treats the maximization of the entropy as a natural starting-point for derivations of other results of statistical mechanics.

The approach of Bryan’s algorithm is to calculate spectra for a range of $`\alpha `$ values and evaluate the probability that the solution is correct given the data and the default model. A weighted average over $`\alpha `$ is then taken.Jarrell and Gubernatis (1996) However, this method may not work well if $`\alpha `$ is very small. In the method developed in Ref. Hague, 2001 a solution produced by Bryan’s algorithm maximum entropy is used as the default model for the next solution. This procedure is iterated until the most probable solution corresponds to an $`\alpha `$ value well within the range of applicability of Bryan’s algorithm.

Since there are two integral transforms involved in calculating $`\sigma (B)`$, then we work withKiatgamolchai et al. (2002)

$$\sigma (B)=\sigma _{XX}(B)+\sigma _{XY}(B)=\frac{1}{2}\sigma _0+\frac{1}{2}_{\pi /2}^{+\pi /2}s(\mu )[\mathrm{cos}(2\theta )+\mathrm{sin}(2\theta )]d\theta $$

where tan$`(\theta )=\mu B`$. This produces a fit to $`\sigma _{XX}(B)+\sigma _{XY}(B)`$ rather than optimally to each component, which could be seen as a drawback. Efforts towards the development of a method which inverts each of the $`\sigma _{XX}(B)`$ and $`\sigma _{XY}(B)`$ tranforms in a semi-independent manner have not been successful so far. However, since $`\sigma _{XX}(B)`$ is an even function and $`\sigma _{XY}(B)`$ is odd, then if both negative and positive magnetic field values are used symmetrically, a fit to $`\sigma _{XX}(B)+\sigma _{XY}(B)`$ unambiguously fits $`\sigma _{XX}(B)`$ and $`\sigma _{XY}(B)`$. This improves results, especially for low mobility carrier gases, as will be seen in Sec. IV.

Since we have assumed discrete forms for $`s(\mu )`$ and $`\sigma (B)`$, then Eq. (III) can be rewritten $`\sigma _i=K_{ij}s_j`$ (with $`M`$ data points and $`N`$ mobility spectrum points). The mobility spectrum may be computed as:

$$s_j=K_{ij}^1\sigma _i$$
(11)
Since the magnetoconductivity $`\sigma (B_i)`$ is relatively insensitive to the details of the mobility spectrum $`s(\mu _j)`$, the kernel contains a large quantity of repeated information; many of the linear equations described by the kernel are (almost) identical.Press et al. (1992) In addition, elements of the kernel matrix which are dominated by signal noise or computational rounding errors are liable to make a huge contribition to Eq. (11).

The dominant effects of data error in the problem can be investigated via *singular value decomposition* (SVD). The $`M\times N`$ kernel may generally be rewritten as $`K=UWV^T`$ where $`U`$ is an $`M\times N`$ column-orthogonal matrix, $`W`$ an $`N\times N`$ diagonal matrix with nonnegative values (the “singular values”) and $`V^T`$ the transpose of an orthogonal $`N\times N`$ matrix $`V`$. As a result of the orthogonalities, the inverse of the kernel can simply be written as $`K^1=VW^1U^T`$.Press et al. (1992)

If one of the elements of $`W`$ is zero then the corresponding element of $`W^1`$ will be zero and the matrix is singular. However, small (non-zero) elements resulting from inaccuracies invert to large values, whereas they should become zeros. It is therefore justified to set values of $`W`$ with magnitude smaller than the data error to zero.Press et al. (1992) SVD reduces the dimensionality of the space that must be searched for a solution giving a massive increase in speed, and discards the effects of noise which would corrupt the solution. It is therefore a very important feature of the following analysis.

A simple, powerful and successful maximum-entropy method for finding a mobility spectrum is described in Refs. Kiatgamolchai, 2000 and Kiatgamolchai et al., 2002, based on the method of Jaynes.Jaynes (1957) The described procedure does not, however, use SVD to remove overspecification and noise and so the calculation time increases with the square of the product of the number of mobility and magnetic field points, $`(NM)^2`$;Kiatgamolchai (2000) nor does it make explicit a hyper-parameter \[$`\alpha `$ in Eq. (10)\] for balancing fit quality against the maximization of the entropy, or deal with error in the data in an obvious way. Also, there does not appear to be any way in which the likelihood of the solution is checked and this leads to overfitting and the creation of artifacts in the mobility spectrum when applied to real data.Myronov et al. (2002)

Minimising $`Q`$ leads to the following relation,

$$\alpha \mathrm{ln}(\frac{s_i}{m_i})=\frac{1}{2}\underset{j}{}K_{ij}^T\frac{\chi ^2}{\sigma _j(B)}$$
(12)
By introducing the SVD to this relation, it can be shown that the $`s_i`$ can be cast in the form of an exponential basis,

$$s_i=m_i\mathrm{exp}(\underset{j=1}{\overset{s}{}}U_{ij}^{(s)}u_j)$$
(13)
where the superscript $`(s)`$ represents matrices in the reduced space.

The solution may then be found in terms of the $`s`$-dimensional $`u_t`$ space rather than the $`N_{output}`$-dimensional $`s_i`$ space. The $`u_t`$ are found iteratively by using a Newton method to obtain the increment in parameter space $`\delta u_j`$,

$$\left((\alpha +ϵ)\delta _{ij}+\underset{k}{}M_{ik}D_{kj}\right)\delta u_j=\alpha u_jg_j$$
(14)
where,

$$g_i=\frac{1}{2}w_i^{(s)}\underset{j}{}V_{ij}^{(s)T}\frac{\chi ^2}{\sigma _j(B)}$$
(15)
and two new matrices,

$$𝐌=\frac{1}{2}𝐖^{(S)}[𝐕^{(S)}]^T\frac{^2\chi ^2}{\sigma _{𝐜}^{}{}_{}{}^{2}}𝐕^{(S)}𝐖^{(S)}$$
(16)
$$𝐃=[𝐔^{(S)}]^T\mathrm{diag}[𝐬]𝐔^{(S)}$$
(17)
are defined to speed up the algorithm: $`𝐌`$ can be calculated once at the beginning of the algorithm, leaving the smaller computation of $`𝐃`$ to the iterative process.Touchette and Poulin (1999)

Many solutions are found for different values of $`\alpha `$ and, by considering the curvature of the parameter space in the vicinity of the solution, the relative probability of the spectrum for a given $`\alpha `$ can be found. Performing the weighted average should then give the most probable mobility spectrum.

$$\mathrm{P}[\alpha |𝐦,𝐆]\underset{\mathrm{i}}{}\left(\frac{\alpha }{\alpha +\lambda _\mathrm{i}}\right)^{1/2}\mathrm{exp}[\chi ^2/2+\alpha \mathrm{S}]\mathrm{P}[\alpha ]$$
(18)
$`\lambda _i`$ are eigenvalues of the matrix, $`\mathrm{\Lambda }_i`$, which describes the curvature of parameter space in the vicinity of the solution,

$$\mathrm{\Lambda }=\mathrm{diag}[𝐬^{1/2}]𝐔^T\mathrm{𝐌𝐔}\mathrm{diag}[𝐬^{1/2}]$$
(19)
and $`\mathrm{P}[\alpha ]`$ (which must be rescalable) is normally given by the Jeffries prior,Jarrell and Gubernatis (1996)

$$P[\alpha ]=1/\alpha $$
(20)
In the BAMS method described below, the calculation time scales as $`N^{1.5}M^{0.6}`$. The SVD scales as $`N^2M`$, and remains a few percent of the calculation time. For input data at 500 magnetic field values and an output spectrum of 300 points (finding solutions at 1000 values of $`\alpha `$) the first BAMS result is produced in roughly 3 minutes on a 1.7GHz Intel Pentium 4 system running Linux, the first few seconds of which are the SVD. Such a number of input points is realistic given automated data-gathering systems; the time-limiting factor in such experiments is often the rate at which the magnetic field can be swept. All previous mobility spectrum analysis methods require that $``$ 90 % of a typical data set were discarded by the user in order that the algorithm would complete in a reasonable time or indeed work at all. The SVD essentially performs this same task (of reducing the space that must be searched for a solution) in a mathematically rigorous manner, removing user bias and also saving time.

## IV Results on Synthetic Data

In order to characterize the BAMS solution method, synthetic data were generated using Eqs. (1)-(5) with realistic parameters and subject to varying degrees of noise. Carrier gases were modelled as Gaussian peaks in $`s(\mu )`$ centered at the specified values. Since the conductivity of the carrier gas is given by the area under the peak \[see Eq. (21)\], the intended sheet carrier density and peak width were also specified for each carrier gas. The *height* of a peak in $`s(\mu )`$ generally has no physical significance.

There were 1000 $`(B,\sigma _{XX},\sigma _{XY})`$ points from $`10`$ T to 10 T in each case, apart from Fig. 2 where a dataset with 500 points from 0 T to 10 T is used for comparison.

The results shown in Fig. 1 (for synthetic data created from a spectrum of two Gaussian peaks with $`\mu _1`$=0.2 m<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> and $`n_1`$=$`1\times 10^{11}`$ cm<sup>-2</sup>, $`\mu _2`$=0.6 m<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> and $`n_2`$=$`1\times 10^{11}`$ cm<sup>-2</sup>; in this case the width of each peak is proportional to the peak mobility) demonstrate how error in the data leads to very little broadening and inaccuracy of peaks in the output spectrum. The iterative procedure where one solution is used as the default model for the next \[see Eq. (8)\] was not necessary in this case. By integrating over each peak (nominating a suitable $`\mu _{peak}`$ value) the number of carriers can be found within each gas:

$$_{peak}s(\mu )d\mu =n_se\mu _{peak}$$
(21)
Additionally, since the Hall sheet density is defined as $`n_{Hall}=(eR_H(B0))^1`$ then from Eqs. (2) and (5):

$$n_{\mathrm{Hall}}=\frac{\sigma _0^2}{e\mu s(\mu )d\mu }$$
(22)
$$\mu _{\mathrm{Hall}}=\sigma _0R_H(B0)=\frac{1}{\sigma _0}\mu s(\mu )d\mu $$
(23)
The true (drift) carrier concentration is simply found by summing the carrier concentrations of each peak:

$$n_{\mathrm{Drift}}=\underset{i}{}|n_i|$$
(24)
so the drift mobility is:

$$\mu _{\mathrm{Drift}}=\frac{\sigma _0}{e_i|n_i|}$$
(25)
A summary of the results from Fig. 1 are shown in Table 1; a simple algorithm was used to find local maxima in the spectra. (Rather than fit a Gaussian to the spectrum to determine the position of the peak, we simply find the highest point: this method is therefore limited in its precision by the number of mobility points chosen for the spectrum.) In addition to the peaks described, there were generally a few much smaller peaks contributing in total to less than 0.5% of the conductivity. (For clarity, not all of the results summarized in Table 1 are shown in Fig. 1.)

Generally, when the peak mobility is overestimated the sheet density is underestimated (and vice-versa) leading to a correct partial conductivity. The Hall mobility compares well with the “ideal” value of 5000cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> at 1.6$`\times 10^{11}`$ cm<sup>-2</sup> (given by the two-carrier Hall-effect equations).Stradling and Klipstein (1990) Even with 3% error in the data the results are acceptable.

With this software (as with that described in Refs. Kiatgamolchai, 2000 and Kiatgamolchai et al., 2002) it is possible to find peaks in the mobility spectrum at mobilities smaller than $`1/B_{max}`$, and this is shown in Fig. 2 and Table 2. The synthetic data feature two carrier gases ($`\mu _1`$=200 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> and $`n_1`$=$`1\times 10^{13}`$ cm<sup>-2</sup>, $`\mu _2`$=1500 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> and $`n_2`$=$`1\times 10^{12}`$ cm<sup>-2</sup>) with 0.01% random data error.

If only positive field values are used, the peaks are found at mobility (density) values of 377 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> ($`5.6\times 10^{12}`$ cm<sup>-2</sup>) and 1533 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> ($`9.0\times 10^{11}`$ cm<sup>-2</sup>). The low mobility peak is not in exactly the correct position, but the high mobility peak (which tends to be more important for real systems) is located accurately.

However, if both positive and negative field values are used the peaks are found to be much closer to the specified values, at mobility (density) values of 226 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> ($`8.8\times 10^{12}`$ cm<sup>-2</sup>) and 1482 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> ($`1.0\times 10^{12}`$ cm<sup>-2</sup>). This is because the use of positive and negative field values fits better to $`\sigma _{XX}`$ and $`\sigma _{XY}`$ whilst the the use of one field direction only fits to $`\sigma _{XX}+\sigma _{XY}`$.

In Fig. 3, which features three carrier gases, the evolution of the spectrum with increasing iteration over default models is shown. The positions of the peaks are summarized in Table 3. With increasing iteration the peaks become too narrow, but the accuracy of the determination of the peak position increases slightly. This demonstrates that many iterations over successive default models is not necessary; it also shows that this mobility spectrum analysis method may not necessarily be relied upon the provide information regarding peaks shapes or widths. Rather than converge on the true spectrum, with increasing iteration over the default model the algorithm appears to converge towards sharp narrow peaks.

This algorithm has also been tested extensively on real data sets. For example, magnetoresistance measurements on the device “6016” presented in Ref. von Känel et al., 2002 has been analyzed. The structure of this device, grown using low-energy plasma-enhanced chemical vapor deposition,Kummer et al. (2002) is shown in Fig. 4.

It features a strained 20 nm quantum well of pure Ge, on a relaxed virtual substrate of Si<sub>0.3</sub>Ge<sub>0.7</sub>. The structure is doped with ten $`\delta `$ spikes of boron 10 nm above the channel. This gives a sheet density in the channel at 4.2 K of 6.2$`\times `$10<sup>11</sup>cm<sup>-2</sup> with a mobility of 87 000 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>.von Känel et al. (2002)

At 300 K there is significant parallel conduction from the doped region, giving a Hall mobility of 1790 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> at a sheet density of 1.8$`\times `$10<sup>12</sup>cm<sup>-2</sup>. We find a result for the channel mobility at 300 K to be 2940 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup> with a sheet density of 5.7$`\times `$10<sup>11</sup>cm<sup>-2</sup> which agrees closely with the quoted mobility value of 3000 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>.

## V Summary

A powerful mobility spectrum analysis method has been presented, based on the application of Bryan’s algorithm to the maximum entropy method. Our method goes beyond a previous maximum entropy mobility spectrum analysisKiatgamolchai (2000); Kiatgamolchai et al. (2002) by using *singular value decomposition* (SVD) to reduce the dimensionality of the search space, and consequently improve the conditioning of the problem. Thus, overspecification and noise in the data are dealt with properly. This means that a large data set of $`1001000`$ points may be used directly without a serious penalty in terms of calculation time. User bias with regard to data point selection is therefore avoided. No other mobility spectrum analysis method can deal with such large data sets without a serious calculation time penalty.

No previous assumptions regarding the form of the result are required, apart from the range over which to search for mobilities. Mobilities can be accurately found which are smaller than $`1/B_{max}`$. Also, since the algorithm works in a reduced space, there is no risk that peaks are lost entirely if insufficient mobility resolution is specified.

This algorithm calculates mobility spectrum over a range of $`\alpha `$ values (where $`\alpha `$ controls the relative importance of $`\chi ^2`$ versus the entropy, that is, between a good fit and a physically reasonable result) and calculates the probability P\[$`\alpha `$\] of each spectrum. Then, the algorithm performs an average of the spectra weighted by their calculated probabilities. The ensures that the solution is the best that can be reasonably deduced from the data given Eqs. (1)-(5). In this way, the results should be relatively free from common artifacts such as mirror peaks, provided that the artifacts are not introduced by systematic measurement errors.Achard et al. (2000)

However, there are a few caveats regarding mobility spectrum analysis in general. It has been suggestedKiatgamolchai (2000) that the shapes of the peaks in a mobility spectrum of a non-degenerate carrier gas could give information regarding the energy-dependence of the momentum relaxation time and therefore the dominant scattering mechanisms. However, the effect on peak shape of different scattering mechanisms is very subtle and we believe that it is unreasonable to expect any useful results from real data. However, if BAMS analysis is performed on data from a range of temperatures then the temperature dependence of the mobility can be examined to give information about scattering mechanisms.

Also, whilst it should be possible to observe “harmonics” in a mobility spectrum due to anisotropy of the effective massMcClure (1956) (for example, in the heavy-hole band of germanium)Goldberg et al. (1957) only Ref. Vurgaftman et al., 1999 seems to have explored this possibility.

Significant intersubband scattering can also invalidate mobility spectrum analysis; in this case it is the intersubband scattering rates rather than the transport scattering rates which must be considered.Studenikin et al. (1999)

One final issue to consider is that the longitudinal magnetoresistance in real data increases monotonically with field, whereas Eqs. (1)-(5) predict that it should saturate.Goldberg et al. (1957) This is a serious issue when analyzing real high magnetic field data, generic to all mobility spectrum techniques, and may relate to the underlying assumption that $`s(\mu )`$ is independent of magnetic field.Argyres and Adams (1956) Often the solution seems to be to assume (possibly unreasonably) that there are mobilities which are much smaller than $`1/B_{max}`$.Contreras et al. (2001) However, using Bryan’s algorithm to balance the least squares fitting error with a physically reasonable result ensures that this mobility spectrum method should minimize such problems.

###### Acknowledgements.

We would like to thank B. Rößner and H. von Känel for help and support, and for making experimental data available. Parts of this work were supported financially by the EPSRC and the INFM. Financial support from GROWTH program ECOPRO No. GRD2-2000-30064 is gratefully acknowledged.