ELECTRICS AND STRUCTURE CHARACTERISTIC TEST OF PHOTODIODE FERROELECTRIC OF FILM BARIUM STRONTIUM TITANATE (Ba0,5 Sr0,5TiO3) BASED ON DIFFERENCE

OF ANNEALING TIME
Abstract Photodiode of Film Ba0,5Sr0,5TiO3 (BST) succeeded to be made with grow BST on the surface of p-type Si(100) substrat with chemical solution deposition (CSD) methode and spin coating technique then at a speed of turning around 3000 rpm during 30 second. Film of BST made with 1 M of consentration and process of annealing at temperature 850C during 8 hour, 15 hour, 22 hour, and 29 hour. Conducted characterization of electrics characreristic, optic charactristic, and structure charactristic of film. Characterization of I-V conducted by illumine and dark condition with colour filters of green, yellow, and red. The obstained result has been indicate that the film have photodiode charactristic. Electrics conductivity ( ) of film with time of annealing during 8 hour, 15 hour, 22 hour, and 29 hour in a series are 1.49 x 10-5 S/cm, 2.05 x 10-5 S/cm, 2.27 x 10-5 S/cm, 6.66 x 10-5 S/cm. Values of stay in a range of semiconductor conductivity, so that the film of BST yielded semiconductor material. Besides I-V characterization and electrics conductivity conducted also characterization of dielectric constants ( ). Value of dielectric constants of film has descend when the voltage improved from 1 V, 2 V, and 3 V. But when the film hold on temperature 850oC by long time duration causes the dielectric constant were ascend. Characterization of optic characreristic among measurement of absorbance and film reflectance. Absorbance curve show wavelength which at most absorbed and reflected that is berween 400-500 nm and 570-600 nm. Data of reflectance film can be used to calculate refractive index (n) and energy gap (Eg). Characterization of structure characreristic in form of examination of XRD. Result which obtained show faction intensity highest by film of BST with time of annealing during 8 hour while faction intensity lowest by film of BST with time of annealing during 29 hour. Keyword : BST, annealing, electrics characreristic, optic characreristic, structure characreristic.

INTRODUCTION Ferroelectric materials are a group of dielectric materials that can be polarized electricity by the internal at a specific temperature range. Polarization occurs in the dielectric as a result of the external electric field and the symmetry in the crystallographic structure in the unit cell. If the material Ferroelectric imposed electric field, then certain atoms are a shift in and cause the dipole moment per unit volume is called dielectric polarization [1]. Materials used in the manufacture of film is barium strontium titanate (BST) and p-type silicon substrate. The increase in annealing temperature would increase the size of crystal grains in the BST films. At annealing temperature

700oC, BST structure can be see as cubic structure with a constant a=3,97 for 30% mol stronsium [2]. XRD instrument provide crystal structure analysis, polycrystalline and amorphous sample, including qualitative analysis and quantitative analysis, indexing design, crystallite size, and texture analysis [3]. XRD method based on characeristic of X-Ray difraction, light scattering with wavelength ( ) when cross crystal slit with distance beetwen crystal line is d. This method give a data that show scattering angel (Bragg angle) versus the intensity. Based on diffraction theory, diffraction angle is depend on width of slit that influence ont diffraction pattern. Whereas, intensity of light diffraction is depend on how much the crystal slit has the same orientation. Purpose of this research is to add BST layer film in p-type silicon substrate surface, and then do electricity, optic, and structure examination on sample. EXPERIMENT METHOD Device that used in this experiment are analitic balance BL 6100, spin coater reactor, mortal, pipet, iwaki measure glass 10 mL, hot plate, scissors, spatula, stop watch, reaction tube, rubber glove, petri dish, tissue, isolation, LCRmeter, I-V meter, oscilloscope, generator function, mask, resistor 10 k. Material that used in this experiment are barium asetat powder [Ba(CH3COO)2,99%], stronsium asetat powder [Sr(CH3COO)2,99%], titanium isopropokside [Ti(C12O4H28).97,999%], methanol pro analysis, 2 metoksi ethanol, dye water, p-type Si(100), Aquades, HF ( fluoride acid), preparation glass and aluminium foil. Substrat that used is p-type Si (100) substrat. BST film maked by sol gel method with mixing barium asetat powder [Ba(CH3COO)2,99%] + stronsium asetat powder [Sr(CH3COO)2,99% + titanium isopropokside [Ti(C12O4H28).97,999%] + strengthen material as precursor and 2 metoksi ethanol as solvent. This experiment use 0.5 as Ba fraction molar, and 0.5 as Sr fraction molar. Then BST ready to plant on silicon substrat surface using spin coater reactor. Next process is annealing and contact assembly. RESULT AND DISCUSSION Caracterization of Current - Voltage (I-V) I-V measurements of the BST films was done in the dark and illuminated conditions with a light intensity of 405 lux. I-V measurement results show that the BST films have been made sensitive to light because of a shift from dark to light when a given voltage from -10 volts to 10 volts as shown in Figure 1.

Currents generated by BST films on the illumine conditions is greater than the dark conditions because of the given light to film causes the film becomes more conductive. The occurrence of conductive properties of the films due to the photon energy from outside is absorbed by electrons. In this condition, the photon energy has a tendency to provide enough energy for the diffusion of electrons, so this resulted in increased diffusion recombination of electrons and increase holes [5, 6, 7]. I-V characterization is also performed by varying the color of the light source by using colour filters of green, yellow, and red. Characterization was carried out to see the film's sensitivity to visible light such as that shown in Figure 1, 2, 3, 4. From the I-V characterization indicated that the film has been made is a photodiode.
2100 ,0

E ec trcs cu rr n t ( A ) l i e m

Figure 1. I-V curve of film that annealed 8 hours (sample A)

5000 ,0

E ec trcs cu rr n t ( A ) l i e m

Figure 2. I-V curve of film that annealed 15 hours (sample B)

51

51

der wolley neerg enimulli krad

01

01

) V( egatlo V

) V( egatlo V

1000,0-

2000,0-

3000,0-

0100 ,0 8000 ,0 6000 ,0 4000 ,0 2000 ,0 0000 ,0 2000,04000,06000,04000 ,0 3000 ,0 2000 ,0 1000 ,0 0000 ,0 5015150151-

E ec trcs cu rr n t ( A ) l i e m

Figure 3. I-V curve of film that annealed 22 hours (sample C)

E ec trcs cu rr n t ( A ) l i e m

Figure 4. I-V curve of film that annealed 29 hours (sample D) Optical Properties of Films Absorbed value of this film if it is associated with the measurements of I-V relations obtained higher the value of absorbance of the film will be produced increasingly large currents. Table 1 shows the value of the refractive index and energy gap of BST films can be sought from the reflectance curves in Figure 5. Energy gap is sought from the graph relation ( h )2 and energy as in Figure 6, 7, 8, 9, with E =hc/ , (description: h is the Planck constant 4.136 x 10-15 eV.s, c is the speed of light 2.998 x 108 m/s, and is the wavelength in meters) [8]. From the table it can be seen the influence of annealing time on the film optical properties. The film, on annealing for 8 hours a percent reflectance and refractive index of the largest, whereas in the annealed films 22 hours a percent reflectance and refractive index of the smallest, meaning that the longer the film at annealing tend to have a smaller refractive index. However, different from the energy gap that ascend when the time of annealing increased.

51

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der wolley neerg enimulli krad

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) V( egatlo V

) V( egatlo V

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3000 ,0 2000 ,0 1000 ,0 0000 ,0 55-

0101-

5151-

Re flca c % ) e tn e (

Figure 5. Reflectance curve of film Table 1. Refractive index and band gap energy of film
Annealing Time of film (hours) 8 15 22 29 Refractive index 1,93 1,64 1,31 1,60 Band gap energy (eV) 2,54 3,12 2,97 3,19

Eg=2,54 eV

Figure 6. Method to measure energy gap of sample A.

31+e5 ,3

Eg=3,12 eV

Figure 7. Method to measure energy gap of sample B.

4 ,3

0 ,3

009

D C B A

2 ,3

elpma S elpma S elpma S elpma S

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008

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6 ,2

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) Ve( y gr en E

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)Ve( ygrenE

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006

2 ,2

0 ,2

0 ,2

005

8 ,1

8 ,1

6 ,1

004

6 ,1

31+e0 ,3

31+e5 ,2

31+e0 ,2

31+e5 ,1

31+e0 ,1

21+e0 ,5

21 +e3

21 +e3

21 +e2

21 +e1

21 +e1

11 +e5

21 01

0 ,0

Figure 8. Method to measure energy gap of sample C.

Eg = 3,19 eV
11 +e5

Figure 9. Method to measure energy gap of sample D. Electrics Conductivity The Film that annealed for 8 hours  conductivity is smaller than film annealed for 15 hours 22 hours  , 29 hours 

  

has electric , .

The increasing of electric conductivity caused by thickness of film is greater along the length of time annealing. The film thickness increase because of increasing size of BST crystal grain, ever done by other scientist with ZnO:Al film [9]. Therefor the size of the crystal grain will affect electric conductivity of film, as same as equation 1 [10].  (1)

Where is electcrical condutivity (S/m), E is energy ( J ), L is size of grain (m), N is consentration of charge carrier (m-3).

2,3

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0,3

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)Ve( ygrenE

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)Ve( ygrenE

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0,2

0 ,2

8,1

8 ,1

6,1

21 +e6 21 +e5 21 +e4 21 +e3 21 +e2

Eg=2,97 eV

21 +e1 6 ,1 0 21 +e3 21 +e3 21 +e2 21 +e1 21 +e1 0

Based on the reference a material called as semiconductor if its electric conductivity about 10-10 S/cm until 10 S/m [11]. From data of the electric conductivity of film can said the BST film is a semiconductor material because electric conductivity of this is about in range the electric conductivity of semiconductor. Dilectric Constant Dielectric constant that obtained when given different of voltage produced different dielectric constant values as shown in table 2. In this research the variation of voltage that used are 1 V, 3 V, and 5 V. Table 2. Konstanta dielectric film value
Annealing time of film (hours) Thickness of film (m) V=1 volt 8 15 22 29 0,442 x 10-6 0,608 x 10-6 1,888 x 10-6 2,157 x 10-6 8,6 18,7 50,1 54,6 Dielectric constants V=3 volt 6,9 13,1 48,4 51,7 V= 5 volt 6,0 12,5 40,4 44,3

From the data, the dielectric constant has been reduced when the voltage increased. This thing appropriate with the equation 2 [12].  Explanation: Q is electric charge (Coulomb), voltage (volt). (2) is capasitance (Farad), and V is

XRD Characterization Figure 10 shows the X-ray diffraction pattern of pure BST films produced. Diffraction peaks are observed indicating particle BST film has a crystal orientation distribution. From the diffraction peaks can be determined miller indices (hkl) with regard as BST crystal structure is a cubic structure [2]. Miller indices obtained can be used to determine the lattice parameters of BST in the tetragonal structure [13]. Strong diffraction of each film occurs in the area (2 0 0) caused by the many area of diffractionon the field (2 0 0) has the same lattice parameters closely spaced, so that the waves experience diffraction is not different phases and tend to be constructive [14]. As can be seen in figure 9 the lowest visible intensity of the diffraction occurs in the area (1 1 0) even in the sample D does not have the area (1 1 0) may be this is due to the area there are only a few area of diffraction. The difference of the four samples prepared is the high intensity of diffraction. Overall the sample had the highest diffraction intensity A. While the lowest intensity of diffraction is sample D. Therefore, sample A has the best crystalline structure than the other samples, because the higher intensity of

diffraction peaks indicates the growing number of the diffraction of a uniform field of in the same field orientation [15]. the other difference is the shift of the diffraction angle in the plane (1 1 0). in this research field (1 1 0) for Ba0,5 Sr0,5 TiO3 occurred in 2 = 31,61 (sample B) whereas other researchers to obtain angle diffraction plane (1 1 0) for Ba0,5 Sr0,5 TiO3 is 2 = 31.99 . A field in the sample (1 1 0) occurs at 2 = 33.74 , diffraction angle is close to the diffraction angle for Sr0,5 TiO3 is 2 = 33.10 , while in sample C plane (1 1 0) occurs at 2 = 30.90 , diffraction angle is close to the diffraction angle Ba0,5 Sr0,5 TiO3 is 2 = 31.15 [16].
Si (100) [200]

[111] [200]

[311]

[110]

[110]*

Figure 10. diffraction pattern of X-ray BST film Table 3. Lattice constant of BST films with tetragonal structure
Annealing time of film (hours) Lattice constant () a=b 8 15 22 29 4,214 4,052 4,017 4,018 c 4,203 4,065 4,008 4,027

Table 3 shows the lattice constant a, b and c films whose value tends to decrease as the length of annealing time. The longer of annealing process will result in crystal grain size of enlarged film as he had done by other researchers [9]. Enlargement of the grain size affects the spacing of atoms in the crystal growing close together, could result in decreased lattice parameter.

D lepmaS C lepmaS B lepmaS A lepmaS 001 08 06

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04

02

CONCLUSION The BST films had been made successfully by the annealing time of 8 hours, 15 hours, 22 hours, and 29 hours at temperature 850 oC that as constant temperature. The results of the characterization of electrical properties of films showed that the films which a photodiode and including semiconductor materials. The electrical conductivity and the constant dielectric films increased by that was followed increasing the annealing time. Therefore it can be inferred long time annealing can affect the electrical properties of films. From the results of characterization of optical properties, sample C absorbed the most visible light, but that wasnt too sensitive to the different wavelengths. After tested the XRD characterization of structural properties can be concluded that the tetragonal structure BST films and the films that had the best crystalline structure of BST films with annealing time for 8 hours. REFERENCES Seo, J.Y, Park, S.W. 2004. Chemical Mechanical Planarization Characteristic of Ferroelectric Film for FRAM Applications: J of Korean Physics society, 45, 769-772. [2] Suvorova, N. A, Lopez, C. M, Irenea, E. A.2004. Comparison of Interfaces for (Ba,Sr)TiO3 Films Deposited on Si and SiO2/Si Substrates: J of applied physics 9, 2672-2673. [3] Omar, M.A. 2007. Elementary SolidState Physics. Addison-Wesley Publishing Inc. [4] Samsiah R. 2009. Characterization Biokomposit Apatit-Kitosan dengan XRD (X-Ray Diffraction),FTIR (Fourier Transform Infrared), SEM (Scanning Electron Microscopy) dan Uji Mekanik. [Skripsi]. Program Sarjana, Institut Pertanian Bogor. Bogor. [5] Hamdani, Komaro M, Rahmat, Irzaman. Uji konduktivitas listrik film tipis Ferielectric LiTaO3 didadah Niobium. Institut Pertanian Bogor, Bogor. [6] Wijaya, S.K.2010.Optoelektronika. Fisika FMIPA UI, Depok. [7] Arief Ardian, Irzaman, Dahrul M, Syafutra H.2010. Uji Arus-Tegangan Film Tipis Ba0,5Sr0,5TiO3 dengan Pendadah Niobium Penta Oksida sebagai Sensor Cahaya, di dalam: Prosiding, 206-212. [8] Pimpabute N, Burinpakhon T, Somkhunthot W. 2011. Determination of Optical Constants and Thickness of Amorphous GaP Thin Film: J. Optica Applicata 41, 259-267. [9] Sinaga P.2009. Pengaruh Temperatur Annealing Terhadap Struktur Mikro, Sifat Listrik dan Sifat Optik dari Film Tipis Oksida Konduktif Transparan ZnO:Al Yang Dibuat dengan Teknik Screen Printing: J. Pengajaran MIPA 14, 51-57. [1]

[10] Seung, Y.M. 2007. Temperature dependence of the conductivity in largegrained boron-doped ZnO films: J. Solar energy Material and Solar Cell 91, 1269-1274. [11] Jorena.2000. Menentukan Energy Gap Semikonduktor Silikon Melalui Pengukuran Resistansi Bahan pada Suhu Beragam: J penelitian sains 12, 19. [12] Giancoli C.Douglas.1998. Physics Fifth Edition. Berkeley : PrenticeHall,Inc. [13] JCPDS.1997. International Centre for Diffraction Data. U.S.A : Campus Boulevard. [14] Tipler, P.A. 1991. Physics for Scientist and Engineers. Worth Publisher Inc. [15] Suhandi, A, Sutanto, H, Arifin, P, Budiman, M, Barmawi.2005. Karakteristik Film Tipis GaAs yang Ditumbuhkan dengan Metode MOCVD Menggunakan Sumber Metalorganik TDMAAs (Trisdimethylaminoarsenic): J Matematika dan Sains 10, 11-15. [16] Remmel T, Gregory R, Baumert B. 1999. Characterization of Barium Strontium Titanate Films Using XRD : J. JCPDS-ICDD, 39-40.

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