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Objective:

The aim of this experiment is to investigate a dummy cell using the FFT impedence spectroscopy and then on the basis of results evaluate the electrical components used in the dummy cell and arrangement of components in dummy cell. Also, use the impedence spectroscopy at dynamic electrochemical system (oxidation of p-Si) for measuring the dielectric properties of the system and then observing the dependence of these properties on the frequency of the alternating current.

Theory:
Impedence (Z)is the resistance to the flow of alternating current. It is the ratio of voltage U and current I. Here U and I are the functions of time and frequency.

Here Um is the amplitude of voltage, Im is amplitude of current, is frequency and is phase shift between voltage and current. Z contain real and imaginary part. Impedence is independent of frequency only for pure ohmic resistors. But capacitor and inductors impedence depends upon frequency. [1]

C is capacitance of capacitor and L is inductance of inductor. Phase shift in case of resistor is 0 but for capacitor phase shift is -90 and for inductor phase shift is 90. A nyquist plot will obtain if we draw imaginary part of impedence against real part of impedence. A Bode plot can also be drawn for any quantity against frequency.

Fig 1: Nyquist plot for Capacitor[1]

Fig 2: Bode Plot for Capacitor[1] Similarly Nyquist and Bode plot for resistor, Inductor and for any combination of these components can also be drawn. [1] Faraday Law of Electrolysis can be used to measure the valance number (z) of the material. z= z is valance number, I current, t is time, M is molar mass, F is Faraday constant and m is mass.[2]

Apparatus and Material:


1. 2. 3. 4. Dummy cell Electrolyte(water + acetic acid with 1:1) p-Silicon FFT Impedence Spectrometer Elypor-02, ET & Te
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Procedure:
Firstly, FFT impedence spectroscopy was used to determine the components and arrangement of components of Dummy cell. Dummy cell was composed of differnet electrical components like resistor, capacitor and inductor etc. Hence a static voltage of 1V was applied to dummy cell for 5 minutes and then impedence of dummy cell was calculated. Secondly, FFT impedence spectroscopy was used to characterize the dynamic electochemical system. The electrochemical system consist of p-Si sample in contact with electrolyte. This leads to the oxidation reaction which consiquently form SiO2. Electrolyte was given negative potential as compared to silicon substrate, while the reference electrode was also imersed in the electrlyte. For this reaction a constant current of 1mA was applied. Finally, Negative potential of -1.4 was applied at the oxidized sample of p-Si to check the impedence of elecctrochemical system in reversed biased direction.

Results and Discussion:


Dummy Cell
In graph 1, Nyquist plot is shown for the dummy cell. Graph 2 is between Zreal and Frequency. With increase in frequency, real part of impedence is decreasing. Where as in graph 3, which is between imaginary part of impedence and frequency, with increase in frequency, Zim is first decreasing and then increasing.

600 500

-Zim 400 [Ohm]


300 200 100 0 0 200 400 600 800 1000 1200

Zreal [Ohm] Graph 1: Nyquist Plot of Dummy Cell


1200 1000 800

Z real

600 400 200 0 0 1 2 3 4 5

log(f) [Hz]
Graph 2: Bode plot of Dummy cell
0 -100

Z im -200 [Ohm] -300


-400 -500 -600 0 1 2 3 4 5

log(f) [Hz]

Graph 3: Bode Plot of Dummy Cell


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From these 3 graphs, one can estimate that the dummy cell is composed of a capacitor and a resistor in parallel manner this is then connected with an other resistance and inductor in series.

Figure: Components of Dummy Cell With increase in frequency, impendence of capacitor will decrease and then more current will pass through capacitor which will consequently short circuit the parallel resistance. That is the reason that we are getting a decreasing curve in graph. From graph 2, one can estimate that the series resistance is of 100 Ohm and parallel resistance is of 1000 Ohm, Because At very high frequency Zreal = Rser = 100 Ohm And at very low frequency, when capacitor will act as insulator then Zreal = Rser + Rpara = 1100 Ohm Rpara = 1000 Ohm Inductor connected in series will not influence because real part of inductors impedence is zero. Graph 3 is showing relation between Zim of dummy cell and frequency. With increase in frequncy, first impendence decreases but after getting a minimum point it starts increasing with more increase in frequency.

Oxidation
Graph 4 is showing the increase in series resistance with time. This series resistance is the resistance of electrolyte. With passing time, there is

not much change in the resistance of the electrolyte. Hence this small change of resistance in system can be ignored.
800 780 760

Rs 740 [Ohm]
720 700 680 660 0 10 20 30 40

time [min] Graph 4: Series Resistance change with time Graph 5 is showing increase in parallel resistance with time. Here parallel resistance is actually the resistance of electrolyte which is inside the pores of oxide layers and reaching to the Si substrate for doing oxidation. With increase in thickness of layer, pores are getting narrower and longer so resistance is increasing. 2 peaks in graph can be seen, which might be due to any noise in the system so we can ignore these.
4500 4000 3500 3000

Rp 2500 [Ohm]2000
1500 1000 500 0 0 10 20 30 40

time [min] Graph 5: Parallel resistance change with Time

Graph 6 is showing decrease in capacitance with time. As time is passing, oxide layer thickness is increasing which in turn decreases the capacitance.

C is the capacitance, A is the area, r is the relative static permittivity, 0 is the electric constant (0 8.8541012 F m1) and d is the thickness of oxide.[3]

C [F]

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40

time [min] Graph 6: Change in capacitance with time As we have pores in our oxide so actuall area is 3 times the area of the substrate getting oxidized. Hence A effective = 3*A = 3* (1cm2) = 3cm2, r = 3.9. Now we can calculate d (oxide layer thickness)
200 150

Thickness [nm]

100 50 0 0 10

time [min]

20

30

40

Graph 7: Thickness of Oxide layer Vs time


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z= z is valance number, I current, t is time, M is molar mass of SiO2, F is Faraday constant and m is mass of SiO2. z=5

Here is etch rate which is zero in our case, is growth rate, Jox is current density and ds/dt is change in oxide thickness with time. From start value of is 0.423 (nm/s)(cm2/mA) and from end it is 0.207 (nm/s)(cm2/mA)

Negative potential:
After oxidation, negative potential of 1.4V was applied to the substrate of p-Si which has developed oxide layer. Graph 8 is showing Nyquist plot in which we have a semi circle in start. This semi circle is due to the parallel impedence of oxide layer and electrolyte in pores of oxide layer. Semi circle starts from some value of Zreal showing the impedence value of electrolyte. After Semi circle there is a sudden increase in the graph which is dur to the formation of space charge region or the deplition zone at the bottom of p-Si substrate because electron from negative potential will combine with holes of p-Si and form deplition zone which will act as capacitor.
Oxide Layer

Figure 3: Negative potential cause formation of Space charge Region

6000 5000

-Zim [Ohm] 3000


2000 1000 0 0 2000 4000 6000 8000

4000

Zreal [Ohm]

Graph 8: Nyquist plot at negative potential Graph 9 is showing the decrease in Zreal with increase in frequency, because at at high frequency impedence of capacitor gets lower and current face less resistance.
7000 6000 5000

Zreal 4000 [Ohm] 3000


2000 1000 0 0 1 2 3 4 5

log(f) [Hz] Graph 9: Bode plot of Impedence real part Graph 10 is showing the decrease in imaginary part of impedence with increase in frequency this first decrease is due to decrease in the capacitance of the depletion region and then the second semi circle is obtained due to the parallel impedence of oxide layer and electrolyte in series with impedence of electrolyte.

6000 5000

- Zim [Ohm] 3000


2000 1000 0 0 1 2 3 4 5

4000

log(f) [Hz] Graph 10: Bode Plot of Impedence imaginary part

Conclusion:
FFT Impedence Spectroscopy is the reliable technique to analyze the static as well as dynamic electrochemical system. It can give precise thickness of oxide layer with time. Hence one can easily study the oxidation phenomenon and apply it in multi fields.

References:
1. Lab manual M208- FFT Impdence Spectroscopy 2. "Faraday's Electrochemical Laws and the Determination of Equivalent Weights". Journal of Chemical Education 31 (May): 226 232 3. College physics by Raymond, vol 10, page # 362

Questions and Answers:


Questtion # 1: What is the role of reference electrode? Answer: Reference elecctrode was used to reduce the ohmic losses in dynamic electrochemical system.

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Question # 2: What Nyquist plot would you expect from a circuit containing an inductor and resistor in parallel configuration? Answer: If we connect a inductor in parallel with a resistor then Impedence will be

Hence, when freqency will be zero then impedence of indutor will be zero and it will short circuit the resistor, making total Z=0 Ohm. But when frequency will be infinity then inductor will act as insulator and Z=Rpara. So Bode plot will be like as given below

Figure 4: Bode plot For Parallel connected Inductor and Resistor Question # 3: In which system can the following Nyquist plot occur? Which is the equivalent circuit.

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Answer: For the above given graph, equivalent circuit will be like given below

Fig 5: Equivalent Circuit Here this should be kept in mind that C1 and C2 should not be equal to each other. Because If it will happen then both semi circle will overlap and we will not be able to distinguish them.

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