Proceedings of 2014 1st International Conference on Non Conventional Energy (ICONCE 2014)

Effect of Boron Doping on Optical and Electrical

Properties of P-Type a-Si:H Films for Thin Film
Solar Cells Application
Chandra Bha] Singh', Sekhar Bhattacharyi, Nafis Ahmed3,
' 2 3 4
, , , SSN Research Centre, SSN Nagar

P.

Balaji Bhargav4

Kalavakkam-603110, TN, India

Icbs.sbc@gmail.com
Abstract- We report the effect of boron doping on optical and

band gap, refractive index and Urbach energy is studied from

electrical properties of p-type a-Si:H films. The p-type a-Si:H

transmittance measurement.

thin films have been deposited by RF-PECVD system varying the

diborane flow rate from 5 sccm to 9 sccm. Enhancement in

II. EXPERIMENTAL DETAILS

deposition rate from 30.3 nmlmin to 33.6 nm reported with

All films were prepared on corning glass substrates using a

increasing diborane gas flow rate. Change in band gap, refractive

index and Urbach energy with varying doping level is studied. An
increase in dark conductivity is reported with increasing boron

RF-PECVD

system

operating

frequency

at

(OXFORD
13.56

PlasmLab

MHz.

Prior

system-IOO)
to

deposition,

substrates were cleaned using DI water, acetone, propanol and

concentration. Solar cells fabricated with 4.63% efficiency.

DI water respectively. After drying, substrates were put on hot

Index Terms-Amorphous silicon, Boron doping, thin film

plat to remove moisture contenpt. Using vacuum pump the

5
pressure of the deposition chamber was achieved near 10-

solar cell, Refractive Index, Open circuit Voltage.

Torr. To deposit the amorphous silicon films, silane gas of 25

I. INTRODUCTION

sccm was used and flow controlled by mass flow controller.

Hydrogenated amorphous silicon (a-Si:H) thin films has

proved

its

importance

in

semiconductor

Here Argon gas was used for dilution of silane gas. The flow

technology

rate of Ar was

applications [1]. Hydrogenated amorphous silicon thin film

solar cells are considered the most promising alternative for
low-cost

renewable

energy

sources

[2-4].

In

thin

Diborane gas was used for boron doping of a-Si:H films.

film

The flow rate of diborane gas was varied from 5 sccm to 9

photovoltaic area, hydrogenated amorphous silicon exhibits

sccm to study the boron doping effect on film's properties. The

different features as compared to the crystalline silicon. While

deposition pressure was maintained at 1000 mTorr during the

various experimental reports are available, there are still few

PECVD growth process. The substrates temperature was kept

aspects of doping of a-Si:H films need to be study. Amorphous

at 250C. All films were deposited at constant RF Power 10

silicon solar cells are fabricated using doped and intrinsic a

watt. Amorphous silicon solar cells were fabricated having p-i

Si:H layers . The p-type and n-type a-Si:H layers are used to

n structure. The thickness of p-i-n layers were 15

generate built - in electrical field in p-i-n device structure. The

and 30

p-type layer highly affects the performance of p-i-n a-Si:H

nm

nm,

350 nm

respectively. Aluminum was used as back electrode

and was deposited using thermal evaporation. Current-voltage

solar cells [5]. The p-type layer is also called window layer for

of solar cells was measured using solar simulator.

device as illumination enters through this layer. In p-i-n solar

The

cells, p-type layer should be highly transparent as well as

transmittance

of

all

films

was

measured

using

Spectrophotometer (Perkin-Elmer UV/VIS Lambda 750) in the

highly conductive. So, boron doping is a very challenging

wavelength range of 300-1200 nm. Thickness and refractive

process to make a-Si:H film as high band gap material, highly

index were calculated by the method developed by Swanepoel

transparent and conductive . It has been reported that Boron

using the transmission data. Optical band gap was determined

dopants change the microstrural properties of a-Si:H films and

from Tauc's equation and Urbach energy was determined from

also growth rate enhancement observed[6-8]. Different gases

Urbach expression using transmittance data.

like BF3, B(CH3)3 and B2H6 are used as p-type dopant sources
for amorphous silicon, microcrystalline silicon and silicon

III. RESULTS AND DISCUSSIONS

carbide films [9-14] .

Fig.l shows the X-ray diffraction pattern of amorphous

In present work, diborane gas is used as p-type dopant

silicon film deposited on glass substrate. Absence of sharp

source to study the boron doping effect on optical and electrical

peak in XRD pattern confirms the amorphous nature of film.

properties of a-Si:H layers. In this study, we investigate the

Fig. 2 shows the SEM image of as deposited a-Si:H film. The

optical properties after increasing the boron doping ratio using

surface morphology of a-Si:H film is homogeneous . The SEM

UV-visible spectroscopy. Effect of boron doping on optical

image of amorphous silicon does not provide any other

information

978-1-4799-3340-2/14/$31.00 2014 IEEE

maintained at 475 sccm, so silane gas

percentage was at 0.05% in Ar-SiH4 gas mixture.

38

regarding

morphology

but

it

confirms

the

ICONCE 2014
January 16 - 17, 2014, Kalyani,

WB,

India.

Proceedings of 2014 1st International Conference on Non Conventional Energy (ICONCE 2014)

N= [B+(B2_ns 2)1/2]1/2

amorphous nature of film which is also confirmed by XRD

pattern.

(1)

where B = 2 ns. (TM-Tm)/(TM.Tm)+ (n/+l)/2, Where n is

the refractive index of deposited film , ns is refractive index of
substrate on which film is deposited, TM is the maximum
transmittance

and

Tm

is

the

minImum

normalized

transmittance at certain wavelength. The thickness of films

calculated from following expression
(2)
Where'd' is the thickness of the film, n], n2 are the
refractive indices at two adjacent maxima (or minima) at
wavelength AI and A2. Fig. 4 shows the deposition rate of

boron doped a-Si:H films with varying the diborane gas flow

rate from 5 sccm to 9 sccm. It is observed that deposition rate

"
2thela

of B-doped a-Si:H film increased from 30.3 nmlmin to 33.6

nm/min.

Fig. I. X-ray diffraction pattern of a-Si:H film.

Similar enhancement in deposition rate of a-Si:H with

increasing diborane flow rate is reported in previous reports
[17, 18]. The enhancement in deposition rate with increasing
diborane flow rate may be due to hydroboron radicals (BH3)
which acts as catalytic sites to increase the sticking probability
of the SiH3 radicals as proposed by Jerome et al [19]. The
refractive

indices

of

B-doped

a-Si:H

films

at

different

wavelength is shown in Fig. 5. The refractive index of film

decreases from lower wavelength towards high wavelength
region.

Decrease

in

refractive

index

is

observed

when

diborane flow rate increased from 5 sccm to 7 sccm but it

again increases from 3.5 to 3.65 at 9 sccm diborane flow rate.

34.0-r------...,

33.5

-6- Deposition Rate

33.0

E
.s 32.5

0::
c
o

Fig. 2. SEM image of a-Si:H film .

E 31.0

Fig, 3 shows the transmittance of as deposited a-Si:H films

a.
Q)

with varying the diborane flow rate.

100,------,
- B2HS = 5 seem

80

---- B2HS = 7 seem

---r---r----l
-r
..
30.0-l--r-....""T""-.-"""T'"
S
7
8
9
5
B2HS Flow Rate (seem)

4.5.-"
""1"'"----,

-B2H6 = 5 seem

20
)(
..
"
.:

O +-T_-,_-,_
400
600
800
1000
1200
Wavelength (nm)

-.-B2H6 = 7 seem

4.0
3.5

&! 3.0

Fig. 3. Transmittance ofB-doped a-Si:H films with varyingB,H6 flow rate .

Deposition rate and refractive index oiB-doped a-Si:H

films:

2.5+-....--.-.___r_--....
...
..-t
600

700

800

900

1000

1100

Wavelength (nm)

Refractive index and thickness of deposited p-type a-Si:H

films were determined from Swanepoel envelop method using

Fig. 5. Refractive index as a function of wavelength ofB-doped a-Si:H thin

film deposited at 5,7, 9 sccmB,H6 flow rate.

transmittance data [15,16].

978-1-4799-3340-2/14/$31.00 2014 IEEE

30.5

Fig. 4. Deposition rate ofB-doped a-Si:H thin films with varyingB,H6 flow
rate

.... 60
...
40

A.

32.0
31.5

39

ICONCE 2014
January 16 - 17, 2014, Kalyani,

WB,

India.

Proceedings of 2014 1st International Conference on Non Conventional Energy (ICONCE 2014)

B. Optical band gap and Urbach Energy:

Where Eu is the Urbach energy and <lo is constant, a is

absorption coefficient and E is photon energy. Urbach energy

The optical band gap (Eg) of the B-doped a-Si:H films were
determined from Tauc's absorption equation [20].
a hu = B (hu- Eg)1/2

is calculated from a plot to In(a) versus (hu), where a is

absorption coefficient of film and 'hu' is the photon energy.

(3)

The reciprocal of the slope of linear portion of (In a) versus

(hu) curve gives the value of Urbach energy. The Urbach

Where a is the absorption coefficient, hu is the incident

energy of B-doped a-Si:H films increases from 349 meV to

photon energy and B is the constant. The band gap was

372 meV with increasing the diborane flow rate from 5 sccm to

calculated from the extrapolated straight line intercept of (a

1
hu)1 2 versus (hu) plot as shown in Fig. 6. Extrapolated linear

9 sccm as shown in Fig.S. Increase in Urbach energy indicates

the enhancement of defects in films with increase of boron

portion intercepts the energy axis (hu) and the interception

concentration.

point is considered as band gap.

B-doped a-Si:H film deposited at 5 sccm diborane flow rate

370

have band gap 1.70 eV. The band gap slightly increased to 1.72
eV for films deposited at higher diborane flow rate 7 sccm.

E
-=

Further increase in diborane flow rate from 7 sccm to 9 sccm

,.,
3S0

cause drastic decrease in band gap from 1.73 eV to 1.66 eV.

Fig. 7 presents the effect of diborane flow rate on refractive

c:
w
-=
u

index and optical band gap. The refractive is measured at 700

nm wavelength. Observed changes in refractive index and band

:5

gap with varying diborane flow rate can be correlated with

350
4 B5 H Flow
S 7 (seem)
8 9 10
2S

Moss's expression Egx nU = constant [21].

-B2H6

Rate

Fig. 8. Urbach Energy ofB-doped a-Si:H thin film deposited at 5,7, 9 sccm
B2H6 flow rate.

5 seem

- - - B2HS = 7 seem

6000

B2HS = 9 seem

4000

-=

:!
C

2000

"

nn

o+-
E
1.6

1.8
2.0
2.2
Photon Energy ,hv(eV)

1.2x107
8.0x10"
4.0x10"

'
- ' 4:i10"

.!r" t:"'"

2.4

2 3 4

Voltage (V)

Fig. 6. Optical band gap ofB-doped a-Si:H thin films with varyingB,H6 flow
rate.
Fig. 9. I-V CURVE of P-type a-Si:H films under dark condition.

1.74-r---4----.- .O

..
..
...
..
.

"0;1.72
w
ci.

..
Cll.70
"
c:
..
01
.. 1.68
"

1.66

c:

.....

..

.. .

")(
"

.
.. .

.
. .E

........

3.8

'E

"
,.

a
't

3.6

13

.
"
E.

:
13
"
"

3.4

-+-Eg
n

6
7
8
B2H6 Flow Rate (seem)

c:
0
0

.,

Fig. 7. Optical band gap and Refractive index ofB-doped a-Si:H thin films
with varyingB,H6 flow rate.

localized state in the films [22]. According to Urbach rule the

C.

absorption edge in the spectral range of direct optical transition

0 5 S 7
B2HS Flow

Rate

(seem)

Electrical Properties
The electrical properties of doped films were studied by

has exponential shape [23, 24]

978-1-4799-3340-2/14/$31.00 2014 IEEE

Dark Conductivity

Fig. 10. Dark conductivity ofP-type a-Si:H films deposited at different

diborane gas flow rate.

Urbach energy is a measure of disorders in films. During

films growth, some defects generated in films which produce

a = <lo exp (E/Eu)

measuring the current under dark condition with a Keithley-

(4)

40

ICONCE 2014
January 16 - 17, 2014, Kalyani,

WB,

India.

Proceedings of 2014 1st International Conference on Non Conventional Energy (ICONCE 2014)

2400 electrometer. The dark conductivity of boron doped a

higher

Si:H films was measured at room temperature. The current

conductivity. We have successfully fabricated a-Si:H solar cell

diborane

flow

voltage curve of films deposited at different diborane flow rate

with 4.63% efficiency.

is shown in Fig.9. The dark conductivity of boron doped film is

rate

shows

an

increase

in

dark

ACKNOWLEDGMENT

increased with increasing boron concentration in film as shown

in Fig.l0.

This work is supported by Defence Research Development

Organization (DRDO), India. The authors would like to thank

D. Solar Cells Fabrications

lIT Kanpur and lACS Kolkata for characterizations.

Amorphous silicon solar cells were fabricated using p-i-n

device structure. The device structure is shown in Fig 11. The

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ICONCE 2014
January 16 - 17, 2014, Kalyani,

WB,

India.