Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands

Within the framework of the dipole approximation the line-shape of light absorption for exciton transitions between broad bands in one-, two- and three-dimensional organic semiconductor structures are calculated. Exciton damping due to lattice imperfections is accounted for as a frequency independen...

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Опубліковано в: :Semiconductor Physics Quantum Electronics & Optoelectronics
Дата:1999
Автор: Grigorchuk, N. I.
Формат: Стаття
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Опубліковано: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 1999
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Цитувати:Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands / N. I. Grigorchuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 25-30. — Бібліогр.: 21 назв. — англ.

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spelling Grigorchuk, N. I.
2017-05-27T09:30:08Z
2017-05-27T09:30:08Z
1999
Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands / N. I. Grigorchuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 25-30. — Бібліогр.: 21 назв. — англ.
1560-8034
PACS 71.35; 71.36; 78.20; S12
https://nasplib.isofts.kiev.ua/handle/123456789/117858
Within the framework of the dipole approximation the line-shape of light absorption for exciton transitions between broad bands in one-, two- and three-dimensional organic semiconductor structures are calculated. Exciton damping due to lattice imperfections is accounted for as a frequency independent parameter. The obtained analytical expressions allow analyses of the line-shape for different space dimensions of structure depending on bandwidth difference, damping parameter and temperature.
en
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
Semiconductor Physics Quantum Electronics & Optoelectronics
Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
spellingShingle Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
Grigorchuk, N. I.
title_short Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
title_full Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
title_fullStr Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
title_full_unstemmed Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
title_sort light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands
author Grigorchuk, N. I.
author_facet Grigorchuk, N. I.
publishDate 1999
language English
container_title Semiconductor Physics Quantum Electronics & Optoelectronics
publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
format Article
description Within the framework of the dipole approximation the line-shape of light absorption for exciton transitions between broad bands in one-, two- and three-dimensional organic semiconductor structures are calculated. Exciton damping due to lattice imperfections is accounted for as a frequency independent parameter. The obtained analytical expressions allow analyses of the line-shape for different space dimensions of structure depending on bandwidth difference, damping parameter and temperature.
issn 1560-8034
url https://nasplib.isofts.kiev.ua/handle/123456789/117858
citation_txt Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands / N. I. Grigorchuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 25-30. — Бібліогр.: 21 назв. — англ.
work_keys_str_mv AT grigorchukni lightabsorptionbyddimensionalorganicsemiconductorsunderexcitontransitionsbetweenbroadbands
first_indexed 2025-11-26T00:08:25Z
last_indexed 2025-11-26T00:08:25Z
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fulltext 25© 1999, Institute of Semiconductor Physics, National Academy of Sciences of Ukraine Semiconductor Physics, Quantum Electronics & Optoelectronics. 1999. V. 2, N 1. P. 25-30. PACS 71.35; 71.36; 78.20; S12 Light absorption by d-dimensional organic semiconductors under exciton transitions between broad bands N. I. Grigorchuk Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, Kyiv, 252028, Ukraine Abstract. Within the framework of the dipole approximation the line-shape of light absorption for exciton transitions between broad bands in one-, two- and three-dimensional organic semiconduc- tor structures are calculated. Exciton damping due to lattice imperfections is accounted for as a frequency independent parameter. The obtained analytical expressions allow analyses of the line- shape for different space dimensions of structure depending on bandwidth difference, damping parameter and temperature. Keywords: low-dimensional organic crystals, light absorption, exciton transitions. Paper received 01.03.99; revised manuscript received 02.04.99; accepted for publication 19.04.99. 1. Introduction Various organic semiconductors (OS) have been a sub- ject of intensive studies for many years. Due to the num- ber of physical effects and their potential applications in electronic and optical devices in newly available materi- als [1]-[3] there has been increasing interest in the inves- tigation of organic structures of low dimensionality [4]- [6]. It is well known [7] - [8] that in contrast to the atomic spectra (or spectra of simple molecules) the spectra of orqanic compounds contain the discrete lines along with the broad bands(∼102-103 cm-1). The nature of these bands attracts the attention of researchers during four last decades. Using a method of selective laser excitation, Personov has shown that at rather low temperatures the broad bands are caused by a non-uniform broadening and in them the huge number of narrow no-phonon lines is hidden. At the same time it was observed [7] that some spectra of the or- ganic compounds embedded in frozen matrices of n-paraf- fins, remain a broadband even at sufficiently low tempera- tures and are not split on numbers of fine lines as one might expect from results of [9]. As a rule, the band broadening in the absence of an ex- ternal action or dephasing processes is connected with the scattering of excitons on phonons, impurities, dislocations and other lattice imperfections reducing the lifetime of ex- citon. For the perfect OS one of basic mechanisms of the exciton energy losses usually comes from their interaction with phonons. Especially, it seems, the multi-phonon pro- cesses may play considerable role in the formation of broad bands. However, phonons not always can give the appre- ciable contribution to the formation of the broad bands in organic structures [10]. At low temperatures the broad band could be expected also due to inhomogeneous broadening of close located no-phonon lines, but for absorption the contribution of such mechanism can practically be neglect- ed [11]. There arise a problem of interpretation of broad bands in OS, which are not split on separate lines at low tempera- tures and not broaden with temperature rising. An attempt to examine this problem for 3D-crystals as well as for the case of narrow exciton bands was under- taken by us earlier in [12-13]. We treated the simple two- band model, in which the distribution of excitons over sub- levels of the lowest band was considered as established, and their photo-excitation to a higher band was studied. This looks like a two-photon problem [14-15], but differs only by the fact, we consider the 1st exciton band as a band of thermalized exciton states. This work represents an exten- sion of techniques previously [12] applied to the bulk ma- terials. In this paper, we apply the above stated approach to calculate the absorption in OS of low spatial dimensional- N. I. Grigorchuk: Light absorption by d-dimensional organic ... 2 6 SQO, 2(1), 1999 ity for another marginal case of broad exciton bands. Using the model mentioned above we have calculated here the contour shape of light absorption for one-, two-, and three- dimensional (1D, 2D and 3D) periodic OS. We also have lead comparison the line shapes of light absorption in OS of different dimensionality. The rest of the paper is arranged as follows. In Sec. 2 we shortly describe our working model and the tasks considered. In Sec. 3 we present the basic formulae for calculation. Section 4 is devoted to the discussion of results and Sec. 5 to the conclusions. 2. Model and main assumptions We study a periodic OS with simple nondegenerate bands whose extrema are located at the center of the Brillouin zone. Every elementary cell contains only one molecule. We assume that the exciton bands are sufficiently sepa- rated and that the configuration mixing of exciton states in each band is absent. The excitons are supposed to be capable to perform a Bloch-wave-like coherent motion. In the media with the large dielectric constant exciton motion can be described by means of the effective mass approximation [16]. According to this approach, the en- ergy of an exciton in the lowest band may be written down as follows ∑ = =        −−= D j ij ij ijii i m k Bk 1 22 ,2,1, 2 )( h ε (1) where {k i1 , k i2 , ..., k iD } are the components of the exciton quasi-momentum vector k i in the D-dimensional space, B ij is the bandwidth of the i-th band in the j-th direction, and m ij is the exciton mass. m ij is connected with the band pa- rameter B ij by means of the relation: 22 / jijij amB h= , where a j is the lattice constant. Using Eq. (1) for ε i (k i ), the distri- bution function of excitons over sublevels of the first exci- ton band one may to express in the form ∏ =         −     = D j m k Tk ijjj D B j j Be manTk kW 1 2 2/2 1 1 2 1 2 12 )( h hπ , (2) where n j is the number of knots in j-th direction and T is the temperature. Hence, in case of broad bands for any dimen- sionality of OS, the excitons in the 1st band can be consid- ered as ordinary gas obeying usual Boltzmann statistics. The transition matrix element from the initial | f 1 k 1 > to the more higher quantum state | f 2 k 2 > (f i describes some other quantum numbers), in the dipole approximation look similarly to that one derived in [12]. The dipole approxima- tion is valid provided the exciton coherence length is much less than the wavelength in organic structure of the absorbed photon. We will neglect the photon momentum as an infinitesimal value comparing with any other pulses in the system. Then for transition frequency we get [ ]∑ = −−Ω≅ D j jjjff akB 1 22 1 2/1 12 δω , (3) where Ω is the energy distance between the bottoms of the first and second exciton bands. Averaging the matrix element over an initial states, which are populated with the statistical weight given by Eq. (2), and summing over all final ones, one finds the prob- ability of transition between examined states. This prob- ability is directly proportional to the dimensionless fre- quency function [12] 2/2 2 )( D B D Tk F     Ω= π ω h × ∫ ∏ ∫ ∞ = − +−ℜ× 0 1 )2/(21D j BitAx jj it jjD edx am edt π π δε (4) which in general form defines the line-shape of light ab- sorption by excitons for such transitions. Here ∑ = Γ+Ω−=−Ω=Ω D j DDjD iB 1 2/, ωεδ , )2/( 2 1 2 TkamA Bjjj h= (5) The boundaries of the 1st exciton band are accounted by second integral of Eq.(4). The symbol ℜ means that the real part of the expression should be taken. Beyond the ex- ponent of Eq. (4) we have omitted the terms of the order of magnitude of equal to, or even higher than the δB/Ω D . This corresponds to the assumption that the energy distance be- tween the first and second exciton bands should much more exceed the difference of their width: Ω >> 2D δB. (6) The damping of the excitons due to phonons or lattice imperfections is accounted for by a frequency-indepen- dent parameter Ã. We also have assumed that δB / à >> 1, (7) i.e., we considered that the difference of two band width is much more than any possible damping in OS. It is necessary to keep in mind, that variable t is dimensional variable (in contrast to another one, x) and is measured in seconds. 3. Basic formulae Let us consider the temperatures for which A j >> 1. Then the integration limits in second integral of the Eq. (4) may be extended to infinity, and using the Poisson integral ∫ ∞ ∞− − = απα / 2 dxe x , equation (4) can be presented as N. I. Grigorchuk: Light absorption by d-dimensional organic ... 27SQO, 2(1), 1999 ×    Ω= 2/2 )( D B D Tk F hω ∏ ∫ = ∞ −         +ℜ× D j j j jjj it B A it Bma edt D 1 0 2/1 21 δδ ε (8) It is easy to see, that the integral of complex conjugate integrand is reduced to integral of Eq. (8) by changing t ⇒ -t. Formally, it allows the integral of Eq. (8) to be represented as a half of the integral in the limits from - ∞ up to ∞. Then the expression (8) may be considered as ex- ponential Fourier transform. Determining the Fourier-im- age for the cases D = 1, 2, 3, we receive then: x xxD xxe F ε παω εα− = ℜΩ=1|)( , (9) ×Ω== yxxyDF ααπω 2|)( [ ])(0 )( 2 1 yxxyIe xyyx ααε εαα −ℜ× +− (10) ×Ω= ⊥⊥= ||||3 2|)( ααπω DF     −−ℜ× ⊥⊥ − ⊥⊥ ⊥ ||||11 || )(; 2 3 ; 2 1 || || εααε εα Fe , (11) where kk Âδ−Ω=Ω , lkkl  δδ −−Ω=Ω , k k k  A δ α 2 = , 2/Γ+++Ω−= i lkkl δδωε , ⊥= ||,;,,, zyxlk , (12) I 0 (x) is the modified Bessel function of zeroth-order with complex argument, 1 F 1 (a,b,z) is confluent gypergeometric function, which, in particular, at a = 1/2, b = 3/2 takes the form [17]: xerf x xF π 2 1 , 2 3 , 2 1 11 =     − , (13) where erf x is the probability integral. The formulae (9)- (11) describe the shape of absorption bands for a general case of an anisotropic lattice: rectangular, as in the case of 2D-semiconductors, or with the allocated symmetry axis, as for 3D-case, for which the cylindrical symmetry was chosen for instance. In the case, when we deal with the isotropic organic structure (the lattice has the square or cubic form) then in the previous formulae it is necessary to put BBB lk δδδ ≡= , ααδ ≡−Ω≡Ω jD BD , , (14) where D describes, as well as above, the dimensionality of the OS. Next, taking in the Eq. (1) into consideration that π 2 lim 0 = → x xerf x , (15) we obtain 2/ |)( 1 )2/( 11 1 Γ+Ω− ℜΩ= Γ+Ω−− = i e F i D ω παω ωα , (16) )2/( 22 2|)( Γ+Ω−− = ℜΩ= i D eF ωαπαω , (17) ×Ω== 2/3 33 2|)( απω DF )2/( 3 32/ Γ+Ω−−Γ+Ω−ℜ× iei ωαω . (18) Thus, the formulae (16)-(18) with accounting of damp- ing describe the band shape, which arise by light absorption in 1D-, 2D- and in 3D isotropic OS. This our result can be reached by another way, when, for example, at evaluating of the second integral in Eq. (4) the saddle-point integra- tion is used. The most simple expressions for the band shape can be obtained in the absence of the damping (à → 0). They are easily appeared from Eqs. (16)-(18). In the other limit case, when the width of both bands coincides, i.e. δB = 0, the absorption curve takes the form of sym- metric Lorentz with the half-width of Ã/2. At last, extracting the real part from Eqs. (16)-(18) we obtain the expressions enabling to calculate immediately the line shape of absorption for various dimensionalities of OS: × +Γ Ω= − = 2/12 1 || 1 11 )1( cos2|)( 1 x e xF x D γ γπγ ×     −+−++ γtan11 1 2 11 2 1 xxxx , (19) ||2 22 2cos2|)( x D exF γγπγ − = Γ Ω= , (20) × Γ Ω= − = ||3 33 3cos22|)( x D exF γγγπγ ×     −++++ γtan11 3 2 33 2 3 xxxx . (21) N. I. Grigorchuk: Light absorption by d-dimensional organic ... 2 8 SQO, 2(1), 1999 In these expressions 2/Γ= αγ , (22) Γ+= Γ Ω− = /2, 2/ 12 1 1 Bxxx δ ω , Γ+= /413 Âxx δ . (23) The region of variable change for x 1 has restriction, which follows from the condition 1 2 11 2 1 2 11tan xxxx −+++≤γ . (24) For x 1 which do not obey the condition (24), the func- tion F(x 1 ) = 0. Analyzing expressions (19)-(21), it is pos- sible to make a conclusion that with increase of the dimen- sionality D of the OS the absorption band, as a whole, is shifted to the short-wave range of a spectrum proportion- ally to the value of 2DδB/Γ. In order to compare the shape of the absorption band for OS of different spatial dimensionalities, we bring in coincidence the origin of the different frequency scales, by setting xxxx ≡== 321 , (25) It means that we have chosen Ω 1 ≈ Ω 2 ≈ Ω 3 ≡ Ω. (26) Such approximation unsignificantly will affect relative intensity of lines, because in accordance with our previous assumption (6), the energy distances between the first and following exciton band much more exceeds width of the 1st band in any of the k-directions. 4. Discussion of results Using the Eqs. (19)-(21), in Fig.1 (A, B) the curves of light absorption for different dimensionality of OS are plotted. All curves correspond to the same certain temperature which enters into parameter γ. The upper panel (A) of the Fig. 1 is consistent with δB/Γ = 8, whereas its lower panel (B) corresponds to the value δB/Γ = 16. Both parts of the figure clearly indicate that under band-to-band exciton transitions with increase of the dimensionality of OS, first of all, the long-wave wing of the absorption band is appreciably changed: the intensity of light absorption is increased and becomes the highest one (for any frequency of this wing) for 2D-semiconductors. For them, the maximum of inten- sity corresponds to the transition frequency ω = Ω − 4δB. For both the 1D and 3D-OS there is an additional shift of the maximum (besides that caused by the difference of the width of two bands) in the direction of the violet spectra range. For 3D-structure this shift somewhat exceeds one obtained in 1D-structure. At given δB/Γ = 8, the relative intensities of lines are the highest ones for 2D-structure and become minimal for 3D-structure. If one chooses the value δB/Γ twice large, then intensity of absorption gets highest for one-dimensional structure, and for three-dimensional one becomes even less (see lower panel of Fig. 1). Most simply the relative intensity of lines could be estimated for one of displayed frequencies. So, for example, at x = 0, with in- crease of dimensionality of OS, it will be described by ratio of: )tan1(2:2:)tan1( γγπγγ +− , (27) which are applicable both for arbitrary temperatures and for any ratio δB/Γ satisfying the condition of Eq. (24). An enhancement of the ratio δB/Γ at fixed temperature results, as it is easy to see from Eqs. (19)-(21), to reduction of γ; consequently, the line intensity is increased in one-dimen- sional case, whereas in two- and three-dimensional cases it decreases only. Moreover, in three-dimensional case this reduction is the most essential. Such tendency maintains also for frequencies close to the frequency of absorption peak and varies only on wings of absorption (see Fig.1). Comparing the absorption curves for the OS of different dimensions (for the same values of the assumed parameters), it should be noted that the line appreciably broadens for transitions from 1D- to 2D-OS. The opposite situation, i.e., a narrowing the line occurs for the transition from the 2D to the 3D case. However, the half-width of the absorption curve Fig. 1. The contour shape of light absorption under exciton transitions between broad bands for 1D-, 2D-, and 3D-dimen- sional organic semiconductors, A = 4: δB = 8à (panel A); δB= = 16à (panel B). -- N. I. Grigorchuk: Light absorption by d-dimensional organic ... 29SQO, 2(1), 1999 in the 3D case remains somewhat larger than one in the 1D case (see Fig. 1, A-, B-panels). The line broadening in the 2D case may be explained by the fact that for normal light incidence the probability of the transfer of excitation be- tween molecules in a plane increases compared to that in a linear chain proportionally to both the number of neighboring molecules and to the wave function overlap. However, in the bulk, this probability is decreased, and the absorption curve is narrowed almost to the width of the 1D structure. This effect is caused by the decrease of the effec- tive bandwidth difference, which may be due to the increase of the effect of exciton dynamics. Influence of the exciton motion on the line-shape of optical absorption was studied in more detail, for example, in [18] and results as a rule in line narrowing. Generally, the line-shape is the product of two factors, the probability for optical transitions between the first and second bands and the Boltzmann distribution of the exci- ton kinetic energies. From Eqs. (19)-(21) it follows that the line-shape of absorption under exciton transitions between broad bands depends in the same measure both on the tem- perature and the width difference of two bands. Moreover, both factors act in the same direction. For instance, the decrease of the difference of δB gives the same result as temperature lowering: the intensity of absorption falls. From the physical point of view, this is due to an equal probabil- ity for an exciton with the defined value of k 1 to scatter on a phonon or an another exciton. The numerical evaluation for 3D-OS exhibits that twofold enhancement of the δB or temperature, results in the decreasing in the intensity of the absorption as much. This our result essentially differs from one obtained earlier [13] for the case of narrow exciton bands. The well known mechanism of inhomogeneous broad- ening due to static disorder in the quasiperfect crystal, seems to play more important role for solutions [7]. An estima- tion may be done by comparing the values of the energy dispersion of one of the exciton levels with the band-width difference δB. The first one is found to be much less for the considered system. The Eqs. (19)-(21) describe the line-shape in the case when the effective masses of an exciton m 1 and m 2 in the first and second bands have positive sings. When effective masses of an exciton are negative then the transition fre- quency, at k 2 = k 1 becomes [ ]∑ = −+Ω≅ D j jjjff akB 1 22 1 2/1 12 δω , (28) hence, replacing in the Eq. (4) the integral over dx on the integral { }∫− ++= π π δ 2 1 )2/(exp yBitAdyi j , (29) one gets the general expression for the line-shape of ab- sorption with negative exciton masses. Further, it is easy to see that at replacement of variable y → π-x, the integral i 1 of Eq. (29) passes in to the last integral of Eq. (4). If one takes into account also that { } TkBTk BB e Z e /3/)( 111 1=− kTr ε , (30) (where Tr is the trace, and Z is the statistical sum) then it becomes clear that the expression for the function F(ω) keeps the former kind as in Eq. (4). This means that for negative exciton masses the shape of absorption curves will be de- fined by the same formulae (9)-(11). Such conclusion is clear from physical reasons as well: under simultaneous changes of the signs of the exciton effective masses in the first and in the second bands, in the case of direct transitions, the energy distances between bands is kept for each of wave vectors of Brillouin zone. For many organic compounds which in experiment dis- play preferentially the properties of individual molecules, our model is invalid. It seems it may hold for those OS which exhibit generally the crystalline properties that are associ- ated with the coherent motion and the band structure [19]. To the last category one may attribute, for example, the low dimensional crystal structure of 1, 2, 4, 5-thetrachlorbenzene, 1,4-dibromnaphthalene, etc. For such OS there are both numerous experiments (e.g., [20]) and numerical calculations (e.g., [21]) studying the light absorption due to the exciton transitions from the ground state to the singlet or triplet ex- citon bands. But we are not aware of any data on the exciton absorption caused by transitions between exciton bands in these OS. Moreover, we are not aware of any experiments on transformation of the absorption line-shape with changing dimensionality of the same material. 5. Conclusions Surmising, we can conclude that within the framework of the two-band model the additional nonthermal broad- ening mechanism arises owing to the difference between the density of states of the bands under consideration. In the case of broad exciton bands, the difference of their widths and temperature of MC are two main comparable factors responsible both for the contour shape and for the intensity of absorption. The increase of band difference gives the same result as an enhancement of the temperature of OS: the intensity of light absorption decreases, and the ab- sorption maximum shifts to the short-wave spectrum range. The absorption contour essentially broadens at transi- tions from 1D- to 2D-OS and is narrowed appreciably at transition from 2 to 3D-dimensionality. Thus, there is an additional shift to the violet spectra range due to the differ- ence of widths of two bands. This shift is proportional to the dimensionality of the structure. Simultaneous changing of the signs of the effective masses does not change the form of an absorption contour. If the state of the lowest band are evenly filled by exci- tons, one can study the states density of higher-lying bands. Benchmark applications to nonlinear exciton-to- biexciton absorption are anticipated. N. I. Grigorchuk: Light absorption by d-dimensional organic ... 3 0 SQO, 2(1), 1999 References 1. T. Tokihiro, Y.Manabe, and E. Hanamura, Superradiance of Frenkel Excitons in Linear Systems // Phys. Rev. B, 47(4), pp.2019- 2030 (1993). 2. Y. Shimoi and S. Abe, Theory of Triplet Exciton Polaron and Photoinduced Absorption in Conjugated Polymers // Phys. 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