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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

The effects of the thickness on the optical constants of CdSe thin films
Mariwan A. Rasheed
Department of Physics, College of Science, Sulaimani University.Kurdistan Reign Iraq.

Abstract
Cadmium Selinide (CdSe) thin films have been deposited on clean glass substrates using vacuum thermal evaporation technique. The optical constants namely refractive index – n , extinction coefficient – k, and dielectric constants – ε1 and ε2 for four thicknesses of 346, 472, 621,and 957nm of CdSe films were studied at a substrate temperature 373K and annealed under a high vacuum at 473K. The extinction coefficient and the imaginary part of the dielectric constant decrease as the thickness increase in certain range of wavelengths.

Keywords:

CdSe, thin films, Optical constants, refractive index, extinction coefficient, dielectric constants.

Introduction
The semiconductor compounds are formed from the combination of two or more elements. The most common compound semiconductors are those formed by the elements of groups symmetrical in respect to the IV group, which is the group of Si, namely, the II-VI (cadmium and zinc chalcogenides), and III-V compounds (gallium and indium arsenides and antimonides). The combination in II-VI compounds gives average four valence electron per atom , which is a situation conductive to the formation of tetrahedral lattice sites provided that there is tendency toward sharing the electrons between atoms. In a compound AB tetrahedral lattice site is the one in which each atom A is surrounding symmetrically by four nearest neighboring B atoms. For this to occur, the B atoms must sit on the corners of the tetrahedron with the A atom at its geometrical

center.However semiconductor compounds are an important group of materials, used in a wide variety of optoelectronic devices including detectors, displays, photovoltaics[1][2][3], and [4], therefore semiconductors are transistors now of increasing importance in modern technology . CdS and CdSe are highly sensitive to visible light, both semiconductors display peculiar features of photoconductivity[5]. Thermal evaporation,[6] sputtering,glowdischarge deposition and chemical deposition techniques have been used for preparing thin films of II-VI compound semiconductors successfully [7][8 ] . CdSe films have been studied in different thicknesses as well as at a various substrate temperatures. Elizalde et al prepared CdSe films of thickness (0.3– 0.5µm)[9]. Nesheva et al found high optical sensitivity of annealed CdSe films of thickness (0.02µm) prepared in room

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

temperature [10]. Nair et al observed the high sensitivity for the annealed films of thickness(0.1–0.5µm) prepared by chemical deposition at (297-323 K ) [11]. Shaalan studied the optical constants of CdSe films and found that the films have the photoresponse in the visible and infrared regions [12]. The envelope technique for the optical transmission spectrum which has been used successfully for determining optical constants for many thin film semiconductors[13-16] will be used to determine n, k, and ε for Cdse thin films prepared in this work.

relation [5]:

d=

Experimental method Determination of thicknesses (d)
Pure CdSe thin films were prepared by a technique of thermal evaporation. A vacuum of about 5×10-6 mbar obtained by using (Edward E 306A) coating system. The required weight of CdSe bulk was charged into a molybdenum boat which is fixed between the two electrodes inside the chamber . A balance of type (Sartorion LA–230 P)was used to the bulk weight. The estimated thickness (d) was found according to the equation;

……… …(2) where n1 and n2 are the refractive indices of the two adjacent maxima (or minima) at the wavelength λ1 and λ2 respectively. These calculations give the films under investigation to have thickness of 346,472,621,and 957nm. In the present work, the rate of evaporation was 30mg/min. Films with thickness 346, 472, 621 and 957nm were deposited on glass substrates having a fixed temperature of 373K. After deposition the films were annealed at 473K under a vacuum for 20 minutes. A cupper constantant thermocouple was used to measure the substrate temperature .

λ 1λ 2 2(n 1 λ 1 − n 2 λ 2 )

Determination of the optical constants
The swanepoel equations were used for calculating the refractive index (n) for film prepared in this work as follows:

 n( λ ) =  N + ( N 2 −  
….(3) where

1 2 2 S )

1 2

  

d=

m 2πR ρ …………….(1)
2

where (m) is the mass of the bulk, R is the distance between the molybdenum boat and the substrate, and (ρ) is the density of the bulk. The thicknesses of the films were controlled by the mass quantity method as mentioned in equation 1. These thicknesses can be calculated through the

 1 1 N = 2S T − T  m M
…...(4) and

 (S 2 + 1) +  2 

S=

 1  1 +  2 − 1  TS  TS  

………

….(5)

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

TM and Tm are the transmission maximum and minimum respectively on the envelope at a certain wavelength. S and TS are the refractive index and transmittance of the clean substrate respectively. The extinction coefficient k can be determined by using the relation ……… …(6) where α is the absorption coefficient which can be written as: ………… …(7) (x) is the absorbance and will be obtained from the relation:

the real and imaginary parts of the dielectric constant respectively. at σ = 0 , k becomes zero ,we get: n2 = ε 1 ………….….(14) Substituting the value of (α) of eq.(7) in eq.(6) then the relation between k, λ, and d can evaluate as:

αλ k= 4π

k=
or

λ x [ −log ( )] 4π d λ d log ( ) 4π x

x α = − log( ) d

……….(15) From eqs.(10 & 11) and neglecting the (-) ive sign in solving k a new relation will be obtained as :

k=

x=

2 Em Em

(

− (n − 1) (n − S ) (n − 1) 3 (n − S 2 )

2

2

2

4

)

1 2

...

...(8)where:

………………(16) Then from eqs.(15 &16) a relation can be obtained for calculating ε as;

k =
2

- ε1 + ε 2

2

Em

..…(9) For calculating the dielectric constant the following relations were obtained from the electromagnetic theory:

 8n S  2 2 3  =  T − n −1 n −S  m 
2

(

)(

)

ε =[
(17)

λ2 8π
2

d log 2 ( ) + ε 1 ]1 2 x

…..

Results and discussion
The optimized optical constants of CdSe films were calculated using transmittance spectra, as shown in Fig.(1).All spectra reveal very pronounced interference effects or photon energies below the fundamental absorption edge. Such behavior of the spectra is evidence of thickness uniformity of the films, otherwise the interference fringes would have been destroyed, resulting in smooth .[5]. transmission curves Fig.(2) shows the observed and calculated transmission spectra of CdSe films as a function of wavelength along

ε = ε1 − iε 2

….

(10)

n 2 − k 2 = ε1

…………(11) ………….(12)

2 nk = ε 2

2nk =

… …….. (13) Where (σ) is the electrical conductivity and (εo) is the dielectric constant of a free space, (ε1)and (ε2) are

σ wε o

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

with the envelope of TM and Tm for all ε1, ε2) respectively on the thickness for films investigated. However, this method different values of λ for CdSe films. has been used successfully for calculating From the figures it is clear also that for refractive index, extinction coefficient, as different values of thickness the decrease well as the dielectric constants of thin in n leads to the decrease in ε for each 1 films[5][13][15]. wavelength . The increase in k leads to an Fig.(3) shows that the wavelength ε2 for each value of dependent of refractive index for various increase in wavelength . thicknesses of CdSe films. Fig.(4) shows the extinction coefficient It is obvious that decrease in n leads to of the films as a function of wavelength decreasing ε1 for each values of λ. for the thicknesses mentioned above. It is As shown in fig.(7) for wavelengths less shown from the figure that the extinction than 1000 nm the refractive indices coefficients are increasing with increasing increase with increasing the thickness for the wavelength in the range of (750– the samples 346,472 and 621 nm. And 1100nm). This figure also indicates that, also the real part of dielectric constant the extinction coefficient depends on increases with increasing the thickness for thickness. It can be seen from the figure the same samples for wave lengths less that for a thicker film the coefficient is than 1000 nm. But the thickness 957 nm is smaller than that for the thinner one. A more photo responsible for wavelengths higher wavelengths region are produce more than 1000 nm . smaller values of k and then Conclusion consequently increases the radiation transparency. 1-The envelope technique for the optical Fig.(5) shows the real part of the dielectric transmissions successfully applicable for constant (ε1) for films having different measuring optical constants in CdSe films thicknesses. prepared by thermal evaporation The imaginary part of the dielectric technique constant for the wave length 2-The optical constants found for CdSe ranges (750-1100nm) for the films at thin film found to be sensitive to is different thicknesses are shown in fig.(6). thickness. This figure shows that the imaginary part 3-The wavelength depend on these of dielectric constant decreases with constants are more sensitive in the lower increasing thickness of the films. wave length than that for the higher. As shown in figures (3 & 5), the decrease in (n) leads to the decrease in ε1 Acknowledgement according to (eq. 14). But the increase in k The author sincerely thanks Dr. Najeeb Toma, in the Physics Department, College leads to an increase in ε2 according to of Science, Salahaddin University for his (eq.12) as shown in figures(4 & 6). Figures (7, 8, 9 , and 10) explain the keen interest in the progress of this work dependence of the optical constants (n , k, as well as offering necessary facilities. Fig.(1): The transmission spectra at different thicknesses (d) of CdSe filmsAt substrate temperatures(373 K) annealed to (473 K) under vaccum: a. 346nm b. 472nm c. 621 nm d. 957nm

2

4

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 400 500 600 700 800 900 1000 1100 1200
T

sample 2

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

T sam ple3

0 400

600

800

1000

1200

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 400

T

sam ple 1

600

800

1000

1200

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 400
T

sam ple 4

600

800

1000

1200

1400

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500 TM sam ple 2 Tm T

2004, 3(1) Part A

600

700

800

900

1000

1100

1200

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500 700 900 1100 1300 TM Tm T sam ple 4

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500

TM Tm T

sam ple 1

600

700

800

900

1000

1100

1200

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500 600 700 800 900 1000 1100 1200 TM Tm T sam ple 3

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

Fig.(2): The observed and calculated transmission spectra of CdSe films as a function of wavelength (λ) for different thicknesses (d): a. 346nm b. 472nm c. 621nm d. 957nm

Fig.(3):Refractive index of CdSe films as a function of λ at different thicknesses

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(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

Fig.(3): Refractive index of CdSe films as a function of λ at different

Fig.(4): Extinction coefficient of CdSe films as a function of wavelength

20 E11 E12 E13 E14 15

10

5 700

750

800

850

900 950 1000 Wave length(nm)

1050

1100

1150

8

between (n) and (d) of CdSe films at different wavelengths Fig.(8): The relation between (1) and (d) of CdSe films at different wavelength

k

(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

Fig.(5): Real part of dielectric constant ε 1 of CdSe films at different thicknesses.

0.25 E21 E22 E23 E24

0. 2

0.15

0. 1

0.05

0 700
3

750

800

850

900 950 Wave  length(nm)

1000

1050

1100

1150

2.9

2.8

2.7

2.6

2.5

1100 nm 1050 nm 1000 nm 950 nm 900 nm

1075 nm 1025 nm 975 nm 925 nm 850 nm

2.4

2.3 250 350 450 550 650 750 850 950 1050

9

8.5

0.056

8

7.5

0.049
7

0.042
6.5

0.035
6

0.028

5.5

0.021

5

1100 nm 1050 nm 1000 nm 950 nm 1100 nm 900 nm 1050 nm 1000 nm 950 nm 900 nm
200 300 400 500 600 700 800

1075 nm 1025 nm 975 nm 925 nm nm 1075 850 nm 1025 nm 975 nm 925 nm 850 nm
900 1000 1100

0.25 1100 nm 1050 nm 1000 nm 950 nm 900 nm 1075 nm 1025 nm 975 nm 925 nm 850 nm

0.2

0.15

0.1

0.014

4.5 1200

0.05

0.007

0 200 300 400 500 600 700 800 900 1000

0 200

400

600

800

1000

9

d (nm)

n between (k) and (d) of CdSe films at different wavelengths

(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

References

[1] Soriaga of CdSe films at different wavelengths n between (1) and (d) M. , Stickney J., Bottomley L., and Kim Y., "Thin films preparationcharacterization , application", 2002, Kluwer academic, Plenum publisher, New York,96. [2] Cassgnol E. , "Semiconductors",1966, Physics and electronics , Philips Technical Library, Netherlands. [3] Ray B., "II-VI Compounds", 1969, pergamom press. [4] Weimer p.,Phy. Thinfilms,2, 1964,147. [5] Soliman L. and Ibraheem A., Fizika , 1997,A6,4,181-189. [6] Rentzsch .R and Bergek H.,"Thin solid film",1976, V.37, 235-239. [7] Chopra K., "Thin film Phenomena" , 1969, Mc Graw-Hill, Inc. [8] Elliott S. , "Physics of amorphous materials",1990, 2nd edition, Copublished in the United States, With John Wiely And Sons Inc. [9] Elizalde E. and Rueda F. ,"Solar energy materials",1986, 13,407 – 418 . [10] Nesheva D. , Aroora D. , Ionov R., "Journal of the electrochem. Soc." , 1993, V. 140, ; P. 2987-97. [11] Nair M., Zingora P. , "journal of Appl, phys",1993 , 74, 2987-2294. [12] Shaalan M., Muller R. , "Solar cells",1990, . 28,; ISS.3 ; P. 185. [13] Swanepoel R. , "J. Phys. Instrum." , 1983, 19-6, Printed in Great Britain. [14] Rassam N. , "Structure, electrical and optical transport properties of evaporated CdSe1-xTex thin films",2000, Ph.D. thesis, Baghdad university, College of education, (Ibn Al-haitham), Physics department,. [15] Makadsi M., Suhail M. and Rassam B. , "Iraqi journal of science",1997,38, 1. [16] Ahmad A. , " Some investigations on thermally evaporated CdS thin films",

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‫,‪(KAJ) Kurdistan Academicians Journal‬‬ ‫4002‬ ‫3( 1 )‬

‫‪2004, 3(1) Part A‬‬

‫.‪2003,M.Sc‬‬

‫.,‪Thesis,University of Salahaddin, Erbil‬‬

‫كاريطةرى ئةستورى لة سةر جيَطيرةكانى رِووناكى‬ ‫تويذالَةكانى‬ ‫)‪(CdSe‬‬
‫مريوان احمد رشيد‬ ‫فيزيا /كوليَجي زانست /زانكوي سليماني / هةريمي كوردستان - عيَراق‬ ‫َ‬

‫ثوختة‬
‫كادميؤم سيلينايد بة ئةستوورى جيا جيا لة سةر ضةند شووشةيةكى خاويَن‬ ‫نيشيَنرا بة هؤى تةكنيكى طةرمية بةهةلَم بوون لة بؤشايدا.جيَطيرةكانى‬ ‫رِووناكى) هاوكؤلَكةى شكاندنةوة ,هاوكؤلَكةى دامركاندنةوةو هةردوو‬ ‫نةطؤرِى نةطةياندن( بؤ ضوار ئةستوورى)759,126,274,643 ‪ (nm‬لة)‪(CdSe‬‬ ‫تويذينةوةي لة سةر كرا لة ثلةى طةرمى‬ ‫)373 ‪ (K‬كة ثاش ئةو ثلة طةرمية لة )‪ (473K‬بة طةرمى هيَل َ‬ ‫رايةوة لة‬ ‫بؤشايدا . هاوكؤلكةى دامركانةوةو بةشة خةيالَيةكةى نةطؤرِى نةطةياندن‬ ‫كةميان كرد بة زيادبوونى ئةستوورى لة مةوداى ديارى كراوى ضةند دريَذة‬ ‫شةثؤليَكدا.‬

‫تاثير السمك على الثوابت البصرية لغشية ) ‪(CdSe‬‬
‫مريوان احمد رشيد‬ ‫فيزياء /كلية العلوم /جامعة السليمانية/اقليم كردستان-العراق‬

‫الخلصة‬
‫رسب كادميوم سيلينايد بأسماك مختلفة على ارضيات نظيفة من الزجاج‬ ‫بإستخدام تقنية التبخير الحرارى فى الفراغ . تمت دراسة الثوابت البصرية )‬ ‫معامل النكسار , معامل الخمود , وثابتى العزل ( لربعة اسماك مختلفة )‬ ‫759,126,274,643 ‪ (nm‬من)‪ (CdSe‬عند درجة حرارة )373 ‪ (K‬للغشية والتى‬ ‫لدنت الى )374 ‪ . (K‬ووجدت نقصان كل من معامل الخمود والجزء الخيالى‬ ‫من ثابت العزل عند زيادة سمك الغشية فى مديات معينة من الطوال‬

‫11‬

(KAJ) Kurdistan Academicians Journal, 2004 ) 1 (3

2004, 3(1) Part A

. ‫الموجية‬

Received

.‫وةرطيرا لة 3002/21/41 وثةسةندكرا لة 4002/3/11دا‬ .14/12/2003Accapaad 11/3/2004

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