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Chapter 3
1. Introduction
The amount of solar energy incident on the earth surface every second (1650 TW) is high
er than the combined power consumption by using oil, fossil fuel, and other sources of en
ergy by the entire world community (< 20 TW) in 2005. The solar photovoltaic power
generation are ever increasing in capacity, yet at a lower scale. Thus there is a scope of fur
ther use of solar energy to produce more electricity. For this purpose a demand for a large
scale commercial production of solar cells have emerged. There is a large variety of solar
cell structures proposed with various types of materials, of which p-type c-Si solar cell has
been one of the most popular and widely used in commercial production with screen print
ing technique.
Looking back to the history of solar cell, one can find that, in 1839 Becquerel observed a light
dependant voltage between two electrodes, that were immersed in an electrolyte. In 1941,
first silicon based solar cell was demonstrated and 1954 is the beginning of modern solar cell
research. Since then there has been several proposals for solar cell design, that can lead to
various photovoltaic (PV) conversion efficiencies () of the solar cells. A conventional Si so
lar cell gives 14.7% PV efficiency[1], whereas other designs, for example, back surface field
(BSF) 15.5% [2], rear local contact (RLC) solar cell efficiency ~20%, as reported by NREL.
However these values are not the theoretical or experimental limit, and there is a continuous
effort in improving the efficiency.
2012 Iftiquar et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
106
The c-Si solar cells fabricated on the high quality silicon wafers, having selective emitter on
the front and local contact on the rear surface [3] shows higher , but the required additional
measures to be taken for the production of such solar cells may substantially increase the
production cost.
Presently the cost of the silicon wafer alone covers >20% of the total cost of solar cell produc
tion, so there may be a technology available in future, by which a large scale production of
silicon solar cells from a thin wafer ( < 200m) will be possible
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ponents of the solution and its concentration. With a dilute NaOH solution containing isopropyl alcohol (IPA) and DI-W, the Si(100) oriented smooth wafers can grow pyramidal
surface texture at 80C temperature [6]. The surface texturing was performed by asymmetric
etching of front surface of the wafers, in a dilute alkaline solution, as against the concentrat
ed solution used for saw damage removal. The loss in mass of each wafer were estimated
from the mass of the wafer measured with a microbalance before and after texturing, which
subsequently led to the estimation of the etched thickness of the wafer and hence etch rate.
Optical microscopic observations, SEM images, and laser scanning were the tools that were
used for the characterization of the textured surface morphology. Ultraviolet visible (UVVis) spectrophotometry was used to estimate the retro-reflectivity of the textured surface.
The etching depends mainly on two processes. One is the rate of the reaction at the surface,
and the other is the rate at which reactants diffuse into the surface. These two processes con
trol the overall rate of the micro structural growth during the etching. The anisotropic etch
ants is expected to etch (110) plane at a faster rate than the (100) plane while the (111) plane
etches at a slowest rate [7]. However if chemical composition of the etchant is such that
some insoluble residue is formed during etching process (like oxides etc.) then diffusion of
etchant into the Si will be hindered and hence etching will not happen as expected.
IPA enhances surface diffusion, so a rapid etching can take place in presence of IPA in the
solution [8]. The NaOH etches silicon crystal planes differently, mostly because of different
atomic concentration in different crystallographic planes. So, at a lower NaOH concentration
the selective etching process helps to create textured surface of the wafer. The chemical reac
tion that takes place is as follows,
Si + 2NaOH + H 2 O Na 2SiO3 + 2H 2
(1)
The sodium silicate (Na2SiO3) is soluble in water and thus Si surface remains devoid of any
deposition. At 80oC temperature, (100) planes etch about two orders of magnitude faster
than (111) planes [9]. For a (100) silicon wafer, a solution of NaOH, IPA, DI-W creates square
based four sided pyramids consisting of sections of (111) planes which form internal angles
of 54.7 with the (100) surface.
The degree of isotropy is sensitive to the concentration of the solution. While a 8% NaOH
solution at 80C temperature etches silicon isotropically to achieve a polished wafer surface,
a 2% NaOH, 8% IPA solution at 80C temperature etches anisotropically to a square based
pyramidal surface texture.
2.3. Phosphorus Diffusion for p-n Junction Formation
The thermal diffusion of phosphorus is necessary to create an n-type emitter to the p-type
wafer. The diffusion depends on various factors, of which temperature and gaseous envi
ronment is most important [10]. In oxygen environment and at 850C temperature, the diffu
sion coefficient (D) can be approximated as D~0.0013m2/hr. The phosphorus diffusion
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108
leads to formation of n+ type emitter at the top surface of the wafer. The diffusion was car
ried out in two stages, pre-deposition and drive-in [11-13]. At the pre-deposition stage, liq
uid POCl3 was evaporated by bubbling N2 gas into the liquid. The POCl3 evaporates and
gets deposited at the surface of the wafers. In presence of oxygen, phosphosilicate glass
(PSG) is formed at the 850C temperature. Phosphosilicate glass or PSG is phosphorus dop
ed silicon dioxide, a hard material formed at the top surface of Si wafer. PSG formation rate
is about 15nm in 30 minutes.
After that, in the drive-in stage, the wafers were heated at 850C temperature for 7 mins,
0.3Torr pressure in presence of oxygen, when the P atoms from the n+-type top layer diffus
es deeper into the wafer, forming a deeper junction. Details of the reaction is given below
(pre deposition)
(2)
(3)
(4)
(5)
For gaseous diffusion with POCl3, the p-type silicon wafers were loaded into a quartz boat,
which was slowly moved into the middle of a fused quartz tube in a heated horizontal fur
nace. The boat, which can hold tens of wafers, was moved slowly into the tube so that the
wafers do not suffer large temperature gradients and warping. Furnace temperature for the
diffusion was held at about 800C, with a variation across the length of the boat of not more
than 2C.
When the PSG was deposited in the pre-deposition stage, the dopant profile leads to a shal
low junction depth and a high surface concentration. In the drive-in stage, a deeper junction
was formed as phosphorus atoms diffuse deeper, thus thicker emitter and a lower surface
concentration of dopant was achieved. The junction depth is defined as the depth where the
phosphorus and boron concentrations are equal (as boron already existed in p-Si wafers).
Table 1 shows details of P-diffusion process. A shorter pre-deposition of only 7 minutes at
850C and a drive-in of about 20 min at 850C temperature, shows good result. It is to be
noted that, a relatively deeper junction and the dead layer near the top wafer surface de
grade blue response of solar cells. The PSG was removed by washing the wafer in a 10% HF
solution for one minute.
The heated quartz tube, used for pre-deposition and drive-in, were periodically cleaned
with HCl vapor in an N2 stream.
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Table 1. A typical condition for phosphorus diffusion used in this study, using POCl3 vapor as a source gas, here lpm
stands for liter per minutes.
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110
SiNx can also be deposited on Si surface through forming gas annealing at a higher tempera
ture. Forming gas is a mixture of hydrogen (H2) and nitrogen (N2), that were obtained by
dissociating ammonia (NH3) at high temperature. In this case the Si atom of SiNx come from
the surface atoms of Si wafer. However, due to higher process temperature, this method was
avoided, as a higher process temperature may alter distribution of phosphorus atoms and
hence the junction depth.
The recombination rate (Us) at the surface, with surface recombination velocity (S), is related
to excess concentration of minority carriers (ns) at the surface. Us S ns. Therefore, the
recombination can be minimized by a reduction of minority carrier type at the surface. Us
ing high-low junction n+pp+ structure the minority carriers at the surface can be reduced
[20]. This technology, known as back surface field (BSF), is widely used at the rear surface of
solar cells. Another method is the field effect passivation. The fixed charges in a passivation
layer repel the minority carriers or the extremely large fixed charges bend the energy band,
resulting in an inverting layer at the surface.
The effective lifetime of charge carrier can reflect total effect of bulk and surface recombina
tion. For the p-type silicon wafer of thickness W and diffusion coefficient of electron Dn, hav
ing front and back surfaces equally passivated, the effective lifetime ( eff) can be expressed
as
(6)
and
(7)
where b is minority carrier lifetime at the back surface. By combining the two cases, the ef
fective lifetime can be calculated by using above equations with about 5 % deviation from
the exact solution [21]
(8)
If the parameters, such as bulk lifetime of silicon (), wafer thickness, and diffusion co-effi
cient of electron are considered to be constant, the measure of effective lifetime gives the di
rect measure of S. As the S is an indicator of surface passivation, the measured eff can also
be used as an indicator of the quality of surface passivation in silicon substrate.
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2.6. Metallization
In order to reduce the production cost of the photovoltaic solar cell, metallization was realiz
ed by screen-printing of metal paste on the SiNx coating, followed by a co-firing. Another
competing technology for solar cell production is buried-contact technology, that involves
laser grooving and metal plating, which is a bit complex procedure, time consuming and
may result in a significantly high number of faulty solar cells, because of small imperfection
in metallizations, a kind of imperfection that does not make screen printed solar cells faulty.
Screen-printing (SP) is cost effective, robust, simple, inexpensive, and fast method of metalli
zation of the solar cells [22-23]. It can also be easily automated with a high throughput (ex
ceeding about 1,000 wafers per hour). This technique has been widely used for solar cell
fabrication since the early 1970s.
For selective emitter formation at the back, etchant material was screen printed before
screen printing the metal paste. During the co-firing process the necessary electronic connec
tion of the cell layers with the electrodes were formed. We used the Ferro- 53-102 aluminum
paste and Ferro-33-462 as Ag paste.
Baking of the screen printed wafers were carried out immediately after each printing step in
a separate conveyor belt furnace at 150C. A burn-out process removes the organic binders
from the paste and it was carried out between 350 ~ 510C.
The thickness of the Al over the entire back surface of the cell was maintained almost uni
form with a variation of 2 m. Wafer bowing is a problem with full Al printing at the back
of the wafer, that was minimized to a level below 0.5 mm due to the use the low bow, lead
free paste and a thicker wafer (300m). Bowing happens mainly due to difference in the
thermal expansion coefficients of Si and Al pastes (Si = 7.6 K-1, Al = 23.8 K-1) and can be
avoided by the local back contact (LBC) approach. For the application of this LBC technique
in industrial production, an addition step of Ag / Al printing in a pattern of two wide bus
bars on the back surface was introduced in order to make back metal contact solderable dur
ing the module making process. Despite the simplicity and technical advantages of this
process for making fully covered back metal contact and surface passivation through back
surface field (BSF) in a single shot, the emerging trend of using thinner wafers to meet the
challenges posed by depleting silicon feedstock may put this process at stake.
A problem of Aluminum ball formation was observed during the co-firing process, that was
mostly eliminated by flowing sufficient oxygen during the co-firing and also by applying a
rapid cooling approach at the end of co-firing.
Metallization is a very important step for device fabrication because it strongly affects per
formance of the solar cell on its short circuit current density (Jsc), open circuit voltage (Voc),
series resistance (Rs), shunt resistance (Rsh), and fill factor (FF). At the front surface the metal
lization creates electrical connection to thin n+ layer that is covered with SiNx. At the back
surface it provides an electrical connection and at the same time it creates a p+ layer. A glass
frit present in the Ag paste makes a superior metallization through SiNx film. However, op
timization of the co-firing process is critical in obtaining desired metal contact. The peak tem
111
112
perature and ramp-up rate during the co-firing process are crucial along with the belt speed
that determines residual time of the wafers to various temperature zones. A cylindrical proc
ess zone has different local temperature setting and the belt carries the Si wafers at a cer
tain speed. The grid pattern of the front electrode has a significant influence on Rs and FF,
that demands optimization of co-firing process. With an increase in the sheet resistance (Rsheet)
of the emitters, Voc decreases, however Jsc increases, which may be because of the improve
ment of blue-response, more light entering the solar cell active region and the reduction of
recombination in the front surface. At a faster co-firing condition BSF layers and Ohmic front
contacts can preferably be established, because the Rsheet of emitters may remain nearly un
changed. We observed a Voc of around 622mV and FF of 80.6% by Suns-Voc measurement.
Suns-Voc measurement is a method of estimating open circuit voltage from decay character
istics of photo generated charge carriers. This method is generally adopted when physical
dimension of solar cell is different from its standard cell structure. Using the result, we ob
tain an optimized co-firing process.
Fig 1 shows important components of screen printing. The screen is made up of an interwo
ven mesh kept at a high tension, with an organic emulsion layer defining the printing pat
tern. Fig. 1(a) shows a microscopic image of the screen. Printing pattern of the front metal
contact with optimized dimensions (finger width, finger spacing, busbar width, maximum
defined finger length) was developed in the form of a computer- aided design (CAD) as
shown in Fig. 1(b). The screen printer is equipped with optical vision system for proper
alignment. The co-firing was carried out in a conveyor belt furnace (Sierratherm).
Figure 1. a) Microscopic image of the screen used in SP. (b) Design of the front metal printing pattern for the single cSi wafer of size 125mm 125mm (pseudo square).
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Ag Metal
n+ Silicon
( 0.1 0. 8 m )
Spiking
Junction
short
Interfacial
P-silicon
Figure 2. P-N junction of a typical solar cell with Ag metallization on front surface showing the possible cases of
shunting through the p-n junction during co-firing as well as good sintering.
113
114
The co-firing was carried out in the condition of sufficient dry and filtered air flow into the
furnace. It is one of the most sensitive steps of the solar cell fabrication. Any non-uniformity
in surface cleaning, texturing, doping, or even ARC can have detrimental effect on the per
formance of the fabricated cells as well, especially in industrial process. If co-firing is done at
a temperature below optimum temperature profile, it results in high series resistance and
hence low FF due to poor Ohmic front contact and poor BSF, whereas over co-firing at a
higher temperature profile may result in junction shunting and degradation in surface and
bulk passivation. Thus, finding an optimum co-firing temperature profile should be always
the first priority in the industrial process.
An advantage of an LBSF compared to the standard full Al-BSF is the lower consumption of
expensive printing pastes. In order to accomplish the local back contact in solar cells, many
techniques have already been employed. It has been shown that the hybrid buried contact
solar cell with photo lithographically defined rear contacts achieves an increase in Voc by
30mV [25] as compared with a standard buried contact cell with conventional aluminum al
loyed BSF, which may result in a high rear surface recombination velocity. Koschier et al.
[26] also demonstrated a 30 to 40mV increase in open circuit voltage relative to conventional
buried contact solar cells using the thyristor structure device on the rear which incorporates
a grown p+ layer in localized regions of the passivating oxide. However, both these rear con
tact schemes require the use of photolithography to remove regions of the oxide to expose
the underlying surface for contact, which may not be suitable for large-scale commercial so
lar cell fabrication processes. Other techniques of creating small area contacts such as laser
firing have been demonstrated to be feasible [27].
2.6.3. Study of rear surface passivation with SiNx film
Recombination of charge carriers at the rear surface in a solar cell can be suppressed by dep
osition of a silicon dioxide (SiO2) layer at the back surface, grown in a high-temperature
(900C) oxidation process [28-29]. Additionally, the SiO2/Al stack at the rear should act as a
reflector for the near band gap photons, that leads to improved light trapping properties
and hence the Jsc of the solar cell may improve as well. Thermally grown SiO2 layers are
manufactured using a time and energy intensive high temperature process, they may not be
a good choice for mass production, although they possibly provide a good thermally stable
passivation [30]. Hence, an alternative low temperature surface passivation became necessa
ry for future industrial production of high efficiency Si solar cells, which should have prop
erties comparable to the SiO2 passivated solar cells.
One way of achieving this is deposition of SiNx layer by PECVD technique. It has been ob
served that this gives comparably low surface recombination velocity (SRVs) as compared to
that with a thermal SiO2 on low resistivity p-type silicon [31-32]. However, conventional
studies have mentioned certain limitations of a SiNx layer on p-type substrates [33]. When it
was applied to the rear of a PERC (Passivated Emitter and Rear Cell) solar cell, the short cir
cuit current density (Jsc) reduced as compared to a SiO2 passivated cell [34]. This effect has
been attributed to the large density of the fixed positive charges in the SiNx layer, inducing
an inversion layer in the c-Si near the SiNx layer. A capacitance-voltage (C-V) measurement
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of SiNx layer having variation of refractive index may demonstrate a part of improvement
with Si-rich SiNx thin film. This may be because of field created by positive charges fixed at
its surface. It is clear that a positive fixed charge is suitable for the n-type substrate, while a
negative fixed charge is suitable for the p-type c-Si wafer substrate.
In this respect formation of local back contact is a promising technique, where a highly dop
ed p-type local back contact can reduce the potential barrier that charge carriers may face
before reaching the metal electrode.
Protection of the back surface of the Si-wafer may be achieved in two possible different
ways, one is a complete coverage with Al back contact, and the other is with SiNx anti reflec
tion coating. The problem with full metal coverage with thinner Si wafers is the cracks and
lattice defects formed during high temperature co-firing when there is high possibility of
wafer bending. Thus partial coverage of the back surface with metal electrode and the rest
covered by SiNx ARC surface passivator is a better alternative.
Figure 3. Comparison of SEM micrograph of the (a) saw damaged wafer surface, unclean and (b) saw damage re
moved clean surface of Cz-Si wafer.
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ing/texturing time of 25, 30, 35, 40 mins, the average specular reflectivities were 17.2, 17.0,
16.1, 15.1%.
Fig. 4 (a ), (b ), ( c ) and ( d ) shows textured wafers with the four different texturing times
and depict the increase in pyramid size with increase in etching time. The average heights of
the pyramids on the surface textured for 25, 30, 35, and 40 min were estimated to be ~ 3, 5, 7,
and 10 m, respectively.
(a)
(c)
(b)
(d)
Figure 4. SEM micrographs of the silicon surface textured for (a) 25 min, (b) 30 min, ( c ) 35 min, and (d ) 40 min in and
solution containing NaOH ( 2 wt. %) in DI-W water and IPA ( 6 wt. %) at 82C.
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Figure 5. Variation of phosphorus (P) concentration with the distance from the emitter surface into the wafer, As ob
served by SIMS depth profiling.
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118
NH3 Flow
SiH4 Flow
Refractive
Deposition rate
(sccm)
(sccm)
index
( /s)
60
18
1.8
2.33
60
30
1.9
2.86
60
45
2.0
4.10
60
60
2.1
4.26
60
66
2.2
4.05
60
75
2.3
4.00
Table 2. Gas Composition in the plasma and the corresponding properties of the as- deposited films. Pressure 1 Torr,
substrate temperature 450C, thickness 80nm.
[O]
[POCl3]
Rsb (/sq)
Rsa (/sq)
300
600
70.5
65.5
400
800
69
64.5
500
100
68.7
63.0
600
1200
65.5
62
Table 3. Comparison of emitter sheet resistance before and after the drive in step for the various different gas flow
rates, where [O] is O2 flow rate and [POCl3] is POCl3 flow rate in sccm, Rsb is sheet resistance before passivation, Rsa is
sheet resistance after passivation.
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improvement in lifetime, from ~ 6 s to more than 10 s, was observed after the phosphorus
diffusion. This improvement reflects the increase in bulk as well as surface recombination
lifetime during phosphorus diffusion. The thermal oxide passivation step after phosphorus
diffusion causes further improvement in lifetime of about ~ 3 s. This improvement can be
attributed to the decrease of surface recombination velocity due to the passivation of surface
by the thermally grown SiO2 layer. The subsequent process of edge isolation by SF6 plasma
causes degradation in the lifetime by ~ 1 s. Such a degradation is basically due to plasma
induced damages, especially near the edges of the wafers that indicates the formation of re
combination centers on the surface during the process. A sharp rise in lifetime by ~ 3 s was
observed after deposition of non-stoichiometric TiOx films [39-40]. It is likely that fixed posi
tive charges in these films bend the semiconductor energy bands near the surface of the wa
fer, which improves the effective surface passivation [41]. A good surface passivation can be
achieved by growing a thin thermal SiO2 passivation layer over TiO2 [39,42,43]. The varia
tion in the minority carrier lifetime during the solar cell fabrication, indicates that the sur
face conditions play a vital role than the bulk of the Cz-Si wafers. During the solar cell
fabrication and before metallization there might have been the improvement in the lifetime
due to gettering of the impurities from the bulk during phosphorus doping. The SiNx films
had a refractive index between 1.90 and 2.13 and a thickness of 65 nm after annealing in the
673-1173 K temperature range. The effective lifetime of the samples became maximum for
the samples annealed at 773 K, while the lifetime of almost all samples, covered with asgrown film, showed a minimum value.
The out-diffusion of hydrogen from the Si-SiNx interface might cause degradation of life
time of the samples if annealed above 773 K in vacuum. The maximum recorded effective
lifetime for the sample passivated with SiNx with a refractive index of 1.94, annealed at 773
K was 55.21 s whereas a minimum lifetime of 6.3 s was found for the sample with as-de
posited SiNx film with refractive index 1.9.
The minority carrier lifetime with different passivating films as AlON, Bare Si, Poly Si, c-Si,
SiOx, a-Si, SiNx were 9.6, 10.1, 21.5, 23.6, 43.4, 51.0, 55.2 s respectively, where all the sam
ples were annealed at 773 K in vacuum.
The comparison of surface passivation of the electronic grade Cz-Si wafers with the different
passivating layers indicates that the SiNx film is superior to other films. In order to identify
the appropriate properties and annealing condition of the SiNx films for solar cell applica
tion, the effective lifetimes of samples, coated with PECVD grown SiNx film, were measured
after annealing at a pressure of ~ 105Pa for ~ 90sec and at temperatures, varying from 500 to
900C in air ambience of a belt furnace. The minority carrier effective lifetime of the silicon
wafers, after the surface passivation with SiNx films and annealed at 500, 600, 700, 800,
900C results in the lifetime of 42, 43, 85, 115, 64s respectively. The annealing temperature
for optimized carrier lifetime was found to be the same (760C) as the set temperature of the
belt furnace at which c-Si solar cell was earlier optimized for co-firing to ensure good Ohmic
contact on the front and back surfaces in conjunction with the proper back surface field
( BSF) generation. Minority-carrier lifetime is a critical parameter for all solar cell designs. If
the silicon wafers to be used for the fabrication of solar cell has a low minority carrier life
119
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time, therefore a short diffusion length, most of the minority carriers cannot be collected,
and the solar cell will suffer from low conversion efficiency.
The results of this study indicate that the proper surface as well as bulk passivation in con
junction with gettering of defects during phosphorus diffusion can lead to a substantial gain
in minority carrier effective lifetime of silicon wafers, provided the degradation of wafer
surface condition during edge isolation is prevented.
3.5. Metallization
3.5.1. Effect of Co-firing Temperature on Solar Cell Performance
In order to optimize the co-firing we defined four different temperature zones in the fur
nace. We investigated each zone, changed stay time of the wafers in each zone, by varying
the belt speed and the temperature of the zones. Emitters were formed with the sheet resist
ance in the range of 30 to 60/sq. A uniform 80nm thick SiNx layer deposited on the front
side served as an anti-reflection coating. Back and front contacts were screen printed on the
wafers and baked. The back contacts were screen printed first, using Al paste, and then the
wafers were dried at 150C for 4min in a belt dryer. Then the front contacts were printed
with Ag paste and the same post-printing treatment was carried out. Then the wafers were
co-fired in a conventional belt-type furnace with four different temperature zones. For the
maximization of the Suns-Voc we varied the temperatures T1, T2, T3, and T4 of the four ther
mal zones. When an optimum temperature distribution was found, we investigated differ
ent belt speeds keeping the temperature unchanged. By measuring Suns-Voc, we determine
the effect of peak temperature change on the FF and Voc. We measured the co-firing temper
atures on the wafers directly in the belt-type furnace with a Datapaq 9000 system, which has
a thin, sensitive thermo couple tip and a thermally insulated measuring system pack for re
cording the firing conditions of a wafer with a thermo couple tip on it. In the first set of ex
periment, without a front electrode, we varied the temperatures T1, T2, T3, and T4 in the
four thermal zones and measured the Suns-Voc.
In the second set of experiments, we examined the effect of varying only the belt speed 170,
140, 165 and 160 inch per minute (IPM) on the Voc for the same sheet resistance. In this step,
we used wafers of 24 m texture, sheet resistance of 35 to 40 /sq. and 80m width of fin
ger with 2.4mm spacing metallization.
In the third set of experiments, we investigated the variation in the Voc with the changes in
the sheet resistance, as obtained in different drive-in operations. In this step, we used wafers
that have 24m texture, sheet resistance of 30, 40, 50, and 60Ohm/sq and 80m as width of
finger with 2.2mm spacing of the metallization. The peak temperature was 759.5C, the
melting duration was 4.5s, and the belt speed was 170 IPM.
In the fourth set of experiment, we investigated firing conditions that determines sheet re
sistance, by varying belt speed, and temperature. We found a co-firing process window that
resulted in a fill factor greater than 77%. For the metallization of the front side, we used Fer
ro 33-501 Ag paste with a peak temperature 700C and a firing time <13s.
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In the fifth set of experiment, we examined the relationship between the number of grid
lines to the series resistance, fill factor, and shading loss in a single-crystal, 5-inch (125mm X
125mm, 154.83cm2) Czochralski-type solar cell. The grid model, as in ref [44], was used to
optimize the grid line design in terms of resistance and shading loss.
In order to obtain higher Voc by BSF layer, we observed that it is necessary to have the rampup rate higher than 70C/s, that resulted in an average Voc higher than 620mV [45], as shown
in Table 4. At a higher ramp-up rate and proper belt speed setting made it possible to get a
higher Voc by reducing the deterioration caused by the effects of the thermal stress on the
wafer. For further improvement in Voc, a densely packed Al layer or uniformly formed BSF
layer created by a high ramp-up rate would also be helpful.
However, as the heat increases, micro-cracks in a wafer or bowing of the wafer may occur,
leading to an increase in leakage current. Large defects or poor features of a wafer increase
the surface recombination and leakage current.
For sheet resistance of 40, 50, 60/sq, the carrier lifetimes were 14, 14.9, 17.2s and surface
recombination velocities were 660, 480, 425cm/sec respectively. We observed that, as the
emitter sheet resistance increases, the carrier lifetime increases with the decrease in surface
recombination velocity. To a certain degree, the variation in sheet resistance is dependant
upon the surface doping density, which is related to electron mobility and its lifetime in a
silicon bulk [46].
Sample numbers
#1
#2
#3
#4
170
140
165
160
70.82
64.13
69.15
72.8
Peak Temp. ( C)
756.5
759.5
765.0
753.0
620.3
617.7
619.0
621.7
FF (%)
79.2
78.9
78.1
80.6
To investigate the effects of different drive-in operations, we examine the variation in Voc
and the Jsc according to the sheet resistance changes. As different drive-in operations for
dopant diffusion can lead to changes in sheet resistance. In this step, we used wafers of 24m texture, sheet resistance of 30, 40, 50, or 60/sq. and 80 m width of finger with 2.2 mm
spacing shows the Voc as 621, 622, 623, 627mV and Jsc as 34.6, 34.9, 35.0, 35.3mA/cm2 respec
tively. The peak temperature was 759.5C, the melting duration was 4.5s, and the belt speed
was 170 IPM.
As the emitter layer becomes thinner the sheet resistance increases, it becomes difficult to
fire the electrode to a moderate depths (i.e., near the pn junction). So the higher sheet resist
ance means thinner emitter and it is more likely to lead to a short circuit of electrodes that
penetrate through the emitter. With low sheet resistance (i.e., a heavy doping) by the over-
121
122
fired sites such a situation is less likely. Fig. 6 shows a safe operating zone for the range of
belt speed (Fig. 6(a)) and firing temperature (Fig. 6(b)), it gets narrower as the sheet resist
ance increases. While the duration of firing was investigated, we found that the shorter the
firing time, the more was the minority carriers lifetime. Thus shorter firing time results in
increased number of minority carriers and as a result increased Voc. It is known that mobility
is dependent on the effective minority carrier lifetime. We also investigated the relationship
between the number of fingers and the series resistance, fill factor, and shading loss in a sin
gle-crystal, 5inch (125mm125mm, 154.83cm2) Czochralski-type solar cell. We used two dif
ferent finger spacings 1.8mm and 2.4mm.
Figure 6. Firing process window from the firing conditions according to the variations of the sheet resistances, the (a)
belt speeds and (b) the firing temperatures. Hatched area indicates the range (min.max.) that has larger than 77% of
the fill factor by the combination of variations of the sheet resistances (drive-in operations), the belt speeds and the
firing temperatures.
The screen printed and metalized front side shading loss is relatively large, in the range of
810% [47]. A grid model suggested in [44] can be used to optimize the grid line design, con
sidering resistance and shading loss. The finger width was as usual 80 m in the case of the
fired Ferro 33-501 Ag paste grid lines. Consequently, the number of grid lines compared to
the original grid line design increased by 17. With the new grid line design, the finger spac
ing decreased from 2.4 to 1.8 mm. This led to a decrease in the total series resistance and an
improvement in the fill factor. The design of the metal grid line was essentially a matter of
finding the separation between the fingers that resulted in the best compromise between
shading losses and resistive ones [48]. The contribution to the series resistance from the dif
fused sheet was 0.192.cm2 for 2.4mm spacing and 0.108.cm2 for 1.8mm spacing, so that
emitter resistance (Re) improved by 0.084.cm2. Each 1.cm2 in series resistance caused a
decrease of about 0.041 in the fill factor (assuming a moderately high shunt resistance) [48],
the total calculated improvement in fill factor due to the increase in emitter sheet resistance
was 0.0078. We also investigated the relation between the variations of Rsheet and spacing
for the available range of more than 77% of the fill factor. As shown in Fig. 7, the narrower
the spacing, the wider range of Rsheet can give a better solar cell. By shortening the spacing
between the grid lines, the series resistance decreased and the FF increased, but the addition
of extra fingers caused a 1% increase in shading loss as well as lowering the short circuit cur
rent. As a result of these drops, cell efficiency reduced from 17.18% to 16.92%.
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Figure 7. The relation between the sheet resistance with finger spacing for the available range of more than 77% of
the fill factor.
Cell Condition
SiNx ARC
PECVD ONO
As-deposited
100
As-deposited
FGA
125
FGA
70
Co-firing
180
Co-firing
165
Si rich SiNx
110
SiON/Si-rich SiNx
As-deposited
205
As-deposited
120
FGA
320
FGA
225
Co-firing
11
Co-firing
20
Table 5. Temperature dependence of different passivating films. FGA forming gas annealing, ONO silicon -oxide nitride -oxide.
For the fabrication of local back contact structure with little modification on conventional
cell process, adaptation of rear passivating film on c-Si solar cell should address two issues
which are
1.
2.
In order to carry out a comparative investigation about the effectiveness of Al-BSF and die
lectric passivation on rear surface, solar cells were fabricated with and without dielectric
passivation in conjunction with screen printed Al grid pattern with different rear metal cov
ered area. Comparative analysis show that the role of the rear surface passivation with SiNx
film becomes dominant when the metal coverage area is below 45% of total surface area.
But, as the metal coverage area goes above 45%, the quality of passivation degrades first
123
124
then starts improving due to the dominating effect of Al BSF over the passivation with SiNx.
As the metal coverage area on the rear surface reaches as high as 85%, an improvement in
infrared response with net improvement in Isc by ~ 0.16 A has been observed. This indicates
that there is dominance of Al-BSF passivation in comparison to the dielectric passivation on
the cells fabricated with screen printed local back contact, especially when the rear metal
coverage reaches 45% or more but when the metal coverage comes below 45%, the effect of
the dielectric passivation becomes dominant.
All the results suggest that the passivation with dielectric film on the rear surface is a must
for local back contact formation by screen printing of Al paste whereas the role of such die
lectric passivation becomes significant for Al printed local back contact only if the metal cov
ered area on the rear surface goes below 45%. These results indicate a suitable rear metal
covered area for high efficiency thin c-Si solar cells with local back contact in conjunction
with dielectric passivation with dielectric film of SiNx and were found to be in accordance
with the results obtained by simulation in ref [28].
Figure 8. Comparison of the illuminated current-voltage (LIV) characteristics of the cells fabricated with local back
contact through the opening in SiNx film on rear surface by varying the peak temperature of the co-firing profile, as
indicated with the traces.
Tp (oC)
Rs (m)
FF (%)
(%)
Voc(mV)
Isc (Amp)
825
12
67
11.5
576.2
4.40
850
11
71
12.4
575.6
4.45
875
75
13.0
576.8
4.38
890
24
60
10.1
574.0
4.35
912
16
67
8.4
564.5
3.77
Table 6. Comparison of the performance parameters of the cells fabricated with local back contact through the
opening window on SiNx film on rear surface by varying the peak temperature of the co-firing profile, where Tp is
peak firing temperature.
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When the cells were co-fired keeping peak temperature below 875C, the problem of Al
bead formation was found to have reduced but the cells were found to have under-fired due
to which the series resistance of the cells increased appreciably. The comparison of LIV char
acteristics of the cells with local back contact through the opening in SiNx film, fabricated by
varying the peak co-firing temperature is shown in Fig. 8 and the comparative analysis of
the performance parameters of the cells is shown in Table 6. The co-firing profile with peak
temperature of 875C was found to be the best for SiNx passivation layer in terms of per
formance parameters despite the formation of the Al beads on the rear surface when the cell
was co-fired at this temperature.
The minimum Rs of 8 m and maximum FF of 75% among the cells compared are the evi
dences of the improved front metal contact without over-heating of Ag finger lines in the
case of the cell co-fired with a peak temperature 875C. The bead formation could be mini
mized with the increased belt speed keeping peak temperature fixed at 875C but that test
could not be carried out in our system because of the limitation to increase the belt speed
beyond 180 IPM.
Figure 9. Process sequence of wafer cleaning, saw damage removal and surface texturing of c-Si wafer.
Wafer cleaning for saw damage removal is a fundamental step for c-Si solar cell fabrication.
Texturing the top surface of the wafer reduces reflection loss of incident light, as well as in
creased effective surface area of the wafer for light trapping, light absorption, carrier collec
tion inside the wafer. Surface passivation with silicon nitride layer increases carrier lifetime
and further reduces reflectivity of the top surface as it also works as an anti-reflection coat
125
126
ing. It also gives protection of the sensitive and thin top n+ layer from environmental degra
dation. Co-firing at two different temperatures for the top and the bottom surface of the
wafer may be necessary as top surface needs lowed co-firing temperature than the bottom
one. Because of the thin n+ layer at the top of the cell and thin silicon nitride layer, the Ag
top contact may make electrical shorting through the n+/p interface, if co-firing is done at
higher temperature. The Al/Ag paste that is used for back contact works for electrical con
tact as well as p+ doping of Si at the back surface. Al is a group III element in the periodic
table so it works as a p-type dopant for Si. After the high temperature co-firing, the Si-Al
alloy that is formed at the back of the cell acts as a p+ layer and creates strong back surface
field so the photo generated holes are efficiently collected during light illumination.
Figure 10. Process flow for doping or emitter diffusion of cleaned and textured wafer. The PSG removal can be carried
out after the pre-deposition (as shown above), or it it can be done after the drive in operation. In the latter case the
drive-in can be the third step (the PSG removal will be the fourth step), and all other steps remain in order. The emitter
diffusion for this latter case has been depicted in Table 1.
Out of several approaches to improve the Voc and FF, increasing the ramp-up rate of temper
ature and setting the belt speed along the heating furnace properly, makes it possible to get
a higher Voc. This increase in Voc may be because of reduction in the deterioration due to the
effect of thermal stress on the wafer. In presence of excess thermal stress small cracks in the
wafer may develop, resulting in a high sheet resistance and low open circuit voltage. Thus
optimizing the drive-in condition for low sheet resistance is necessary. The faster belt speed
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in the co-firing stage, results in higher ramp-up rate for temperature, that greatly enhances
Voc. By studying the results of our five sets of experiments, we determined certain ap
proaches for improving the open circuit voltage and fill factor:
1.
As the temperature ramp-up rate went higher, we could obtain better uniformity of the
BSF layer.
2.
A higher belt speed tends to reduce the overall leakage current of a wafer.
3.
As the emitter sheet resistance increases, the open circuit voltage decreases with the de
crease in dopant concentration in the emitter, although the short circuit current is in
creased, that is attributed to the improvement of the short wavelength response, more
light entering the cell active region and to a reduction of recombination in the front sur
face.
4.
The peak temperature of the wafer was optimized for the shorter the firing time. It re
sults in increased minority carrier density, which in turn increases the open circuit volt
age. We investigated the optimal firing conditions for different sheet resistance,
temperature, and belt speed, and within the profile window of the firing process, we
obtained a high Voc (>620 mV) and fill factor (>77%) for a range of different sheet resist
ance emitters.
5.
By narrowing the spacing between gridlines, the series resistance and the fill factor of
the cell got enhanced.
However, the short circuit current falls because of shadow effect of the metal electrodes. In
the case of low series resistance, we can expect to improve the fill factor, while the short cir
cuit current decreased because of the shading loss.
Figure 12. Process steps for metallization of the solar cell by screen printing (SP). In our system, the peak temperature
was 759.5C.
127
128
Author details
S. M. Iftiquar1, Youngwoo Lee1, Minkyu Ju1, Nagarajan Balaji2, Suresh Kumar Dhungel1 and
Junsin Yi1,2*
*Address all correspondence to: [email protected]
1 College of Information and Communication Engineering, Sungkyunkwan University, Re
public of Korea
2 Department of Energy Science, Sungkyunkwan University, Republic of Korea
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