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Second International Conference on Electrical and Computer Engineering ICECE 2002, 26-28 December 2002, Dhaka, Bangladesh

Separation of Photoabsorption in Carbon Layer of n-Carbon/p-Silicon Photovoltaic Cell


Md. Shofiqul Islam1 , Sharif Mohammad Mominuzzaman1 , Mohammad Rusop2 , T. Soga2 Department of Electrical and Electronic Engineering, Bangladesh University of Engineering and Technology, Dhaka-1000, Bangladesh. E-mail: shofiqul@eee.buet.ac.bd 2 Department of Environmental Technology and Urban Planning, Nagoya Institute of Technology, Nagoya, Japan
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Abstract Photoresponse characteristics of photovoltaic (PV) solar cell fabricated from phosphorus (P) doped carbon on p-type silicon (n-C/p-Si heterostructure) have been studied using experimental observations. The carbon layers of the cells under analysis were deposited on p -type silicon substrate using the targets containing various amounts of phosphorus (1% to 7%) by pulsed laser deposition (PLD) technique. Quantum efficiency of these cells is measured in ultravioletvisible-infrared (UV-VIS-IR) region (300-1200 nm). The spectral photoresponse characteristics are observed to vary with phosphorus content in the carbon layer. The overall photoresponse characteristics are deconvoluted using Gaussian distributions. The individual contribution of carbon and silicon region is extracted from deconvoluted spectra in accordance with the optoelectronic properties of the carbon layer, such as, defect density, optical gap, etc. The relative contribution due to photon absorption in carbon region is observed to increases with P content for the cells deposited from the target containing up to 5% P and decreases thereafter whereas, the relative contribution of silicon region shows opposite variation. Keywords Diamond like carbon (DLC), Quantum efficiency, Pulsed laser deposition (PLD), Electron spin resonance (ESR). INTRODUCTION In order to meet up the increasing energy demand of the world, the conventional sources of energy are going to be exhausted in near future. Now the extensive use of huge solar energy could be the remedy in fighting against this energy crisis. Therefore, research on solar cells is getting priority. Although silicon and compound-semiconductor-based solar cells have dominated the market since last few decades, low-cost, stable and high efficient solar cells are yet to be commercially realized due to high material and production cost. However, with the emergence of carbon as semiconductor material the situation is expected to change. Carbon is available in nature and it exhibits some outstanding properties

such as chemical inertness, high hardness, high thermal conductivity, high dielectric strength and infrared (IR) optical transparency. The interesting and unique feature for carbon is that these properties can be tuned over an unusual wide range from that of semi metallic graphite (~0.0 eV) to that of insulating diamond (~5.5 eV) by varying the ratio of sp3 and sp 2 hybridized bonds. Hence carbon has attracted the attention of the researchers for its application in solar cells. Carbon based heterostructures such as metal insulator semiconductor (MIS) diodes [1], Scottky diodes [2], metal insulator semiconductor field effect transistor [3], heterojunction diodes [4], and solar cells [2], [5]-[8] on silicon have already been reported and hence thereby demonstrates the potentiality of carbon materials in electronic devices. However, only few works are reported on the photovoltaic properties of C/Si hetero-structures [2], [5]-[7]. It is worth noting that all the researchers working with carbonaceous solar cells reported the overall photoresponse of their cells. But the separation of contribution of carbon and silicon in a C/Si cell is yet to be realized. At present it is very necessary to work on spectral photoresponse characteristics of the C/Si heterostructures and visualize the contribution separately to understand the nature and improve the characteristics for its practical implementation. Previous study shows that the energy of the carbon species generated by various preparation methods is different and plays an important role in controlling the sp 3 /sp 2 ratio. Again the population of sp 3 and sp 2 bonds in precursor material also dictates the sp3 /sp 2 ratio. Hence the properties of carbon thin films depend on the method of deposition and precursor materials used [9]. Pulsed laser deposition (PLD) process has the ability to generate highly energetic carbon species, which enhances the formation of a high percentage of sp 3 bonded carbon atoms and therefore, deposition of high quality diamond like carbon (DLC) film can be realized. Usually graphite is used as precursor in PLD method. However, carbon thin film obtained by PLD technique using starting precursor camphor (C10 H16 O), a natural source, is reported to have better optoelectrical properties [8]-[10]. Because the presence of huge sp3 sites in camphor molecule assists in forming high quality diamond like carbon (DLC)

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film and the presence of hydrogen ions reduces the defects by passivating the dangling bonds. In this report, we have separated the contribution of carbon and silicon to the overall photoresponse characteristics of n-C/p-Si heterostructure whose carbon layer has been deposited from P-doped camphoric carbon target on p-type silicon substrate by PLD technique. The obtained result has also been compared with various optoelectronic properties of carbon thin films. EXPERIMENTAL DETAILS We have conducted our analysis of spectral photoresponse using the experimental observations of n-C/p-Si heterostructure. The details of deposition of carbon film in order to obtain n-C/p-Si structure has been discussed elsewhere [8]. In short, target is prepared from camphoric carbon (CC) soot obtained from camphor burnt in a quartz tube. The camphoric carbon soot deposited on the inner wall of the tube is collected, dried in an oven and pressed into pellet to be used as target in PLD technique. In order to get phosphorus (P) doped film, red phosphorus is mixed with dried CC soot before pressed into pellet. The schematic of the n -C/p-Si photovoltaic (PV) cell is shown in Fig. 1. Light Gold electrode (15 nm) P-doped CC thin film (170~200 nm) p-type silicon substrate (350m) Gold electrode (100 nm) Figure 1: Schematic of the n-C/p-Si photovoltaic cell. RESULTS AND DISCUSSIONS Experimentally measured quantum efficiency plotted as a function of wavelength in the range of ultraviolet-visible-infrared (300-1200 nm) region is shown in Fig. 2 for different cells whose carbon layers have been deposited from the targets containing various amounts of phosphorus (1%, 3%, 5% and 7% by weight).
0.8 0.7 1% P-doping 3% P-doping 5% P-doping 7% P-doping 0.5 0.4 0.3 0.2 0.1 0.0 200 400 600 800 1000 1200

It is seen that overall response improves with the P content in the carbon layer for the cells deposited from the target containing up to 5% P. The response of the cell with 7% P in the target degrades. It is also seen that for 7% P cell the occurrence of peak absorption shifts to right than that of other cells. The individual contribution of carbon and silicon has been extracted from the above overall spectra by using curve fitting technique. The spectra have been fitted with different combinations of Gaussian and Lorentzian distributions. Among them the fitting with three Gaussian distributions approximates the experimental observations more accurately. A typical deconvoluted spectra for the PV cell containing carbon layer deposited from the target containing 1% P is shown in Fig. 3 where the first Gaussian curve occurs with peak at the wavelength of 525 nm. Similarly, second and third Gaussian curves occur with the peaks at 740 nm and 960 nm respectively. Since the area under the spectral photoresponse is related with short circuit current and short circuit current is related with overall performance of the cell, we have used the area under individual Gaussian spectra in order to extract the individual contribution of carbon and silicon.
0.5

Experimental data

Quantum efficiency

0.4

Fitted overall spectra Second

0.3

Third

0.2

0.1

First

0.0 200

400

600

800

1000

1200

Wavelength (nm)

Figure 3: Photoresponse of 1% P cell fitted with three Gaussian distributions. Results obtained from fitted spectral response of all the cells under analysis show that for first and second Gaussian curves, area and width exhibit prominent variation with P content whereas, the third Gaussian curve shows insignificant change. Since the dopant concentration in the carbon layer of the n-C/p-Si PV cell is varied and deposited on same type silicon substrate, the absorption spectra due to photon absorption in silicon region should not change. The peak position of the third Gaussian curve (around 950 nm) lies in the range of peak position of standard silicon absorption spectra [11]. Therefore, the third Gaussian curve might be the spectra due to photon absorption in silicon region and the remaining two curves are for the absorption in carbon region. Figure 4 shows the relative contribution of carbon region as a function of P -content in the target. The

Quantum efficiency

0.6

Wavelength (nm)

Figure 2: Spectral photoresponse of n-C/p-Si cells with different P-doping.

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extracted result exhibits that the relative contribution of carbon region increases with P content up to 5% P cell and decreases thereafter. Accordingly, the relative contribution of silicon region shows opposite nature (Fig. 5). Now this extracted result of carbon contribution can be correlated with various properties of P-doped CC thin films.

spectra. It is observed that the variation pattern of carbon area is similar to that of total area and they are very close to each other whereas silicon area shows negligible change (Fig. 6). This indicates that carbon is dominating the overall performance of the cell.
300

Total Carbon Silicon

Area (Response)

250 200 150 100 50

Contribution of C (%)

86 84 82 80

78 76 1 2 3 4 5 6 7 8

% P content

Figure 6: Absolute contributions as a function of P content in the target used for the deposition of carbon layer. Previous study shows that overall efficiency and fill factor of the cells under analysis increase with P content up to 5% P cell and decrease thereafter [7]. That is, the trend of variation is similar to that of carbon contribution and this is expected since carbon region dominates the overall performance. Figure 7 shows the variation of field width at half maximum (FWHM) for three Gaussian curves as a function of P content in the target. FWHM1 corresponds to the width of first Gaussian curve. Similarly, FWHM2 and FWHM3 are the widths of second and third Gaussian curves respectively.

% P-doping

Figure 4: Contribution of carbon region of n-C/p-Si cell as a function of P content in the target used for the deposition of carbon layer.
Contribution of Si (%)

30

25

20

15

Width at half maximum (nm)

10

% P-doping

280 260 240 220 200 180 160 1 2 3 4

FWHM1 FWHM2 FWHM3

Figure 5: Contribution of silicon region of n-C/p-Si cell as a function of P content in the target used for the deposition of carbon layer. From electron spin resonance (ESR) spectroscopic analysis it is found that defect density of the films decreases with P incorporation [9]. With the decrease of defects, the absorption due to defect states decreases and hence the effective optical response should increase with the P content, which is consistent with the increasing nature of carbon contribution up to 5% P cell. It is found that optical gap of CC film remains approximately unchanged for the films deposited from the target containing up to 5% P and decreases thereafter [12]. The contact potential of the C/Si cell is related to the optical gap of the carbon layer. Again the photovoltaic performance of the cell is related to the contact potential. Hence the decreasing nature of carbon contribution for 7% P cell can be explained with the declining nature of optical gap for the film with 7% P in the target. Absolute contributions are estimated from calculating the areas under individual and total

% P content in the target

Figure 7: Field width at half maximum of three Gaussian curves as a function of P content in the target used for the deposition of carbon layer of n-C/p-Si cell. The first and the second curves exhibit prominent change in widths with P content in the target. This might be due to the change of gap-states with the variation of P content in the target. But the third curve exhibits insignificant change in width. This indicates that the width of the spectra for silicon region remains almost constant. It is e xpected because none of the parameters of silicon region is being varied. Diamond like carbon (DLC) contains more sp3 bonds than that of graphite. Since the band gap of diamond is larger than that of graphite, the more the

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sp 3 bonds the more is the band gap and hence the occurrence of peak absorption at lower wavelength. Therefore, it may be predicted that the first Gaussian curve is related to the contribution of sp3 bonds and the second Gaussian curve is for mixture of sp3 and sp 2 bonds. CONCLUSIONS From the analysis of P -doped CC/p-Si cell it is seen that relative contribution of carbon increases with P content up to 5% P cell and decreases thereafter. The decreasing nature of carbon contribution might be due to the creation of gap states and decrease of the optical gap of the carbon layer for higher amount of P content (above 5% P). Correlating this obtained result with the optoelectrical properties of CC thin films it can be concluded that as long as the carbon layer remains diamond like in nature with the addition of P, the contribution of carbon region increases. Too much addition of P deviates the carbon layer from its diamond like nature and the performance degrades. Again from the absolute contributions of carbon and silicon region as compared to total response, it is observed that carbon is dominating the overall performance of the cell. Again the prominent variation of the area, width and peak position of the first two Gaussian curves signifies the change in ratio of sp3 and sp 2 bonds with the addition of P in carbon layer. We know the more the sp3 bonds the more is the band gap and hence the occurrence of peak absorption at lower wavelength. So the first Gaussian curve may be predicted as the contribution of sp3 bonds and the second Ga ussian curve may be for mixture of sp3 and sp 2 . REFERENCES

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