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Atmospheric pressure chemical vapor deposition of silicon thin films using

cyclohexasilane

Conference Paper · June 2014

DOI: 10.1109/PVSC.2014.6925583

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Guruvenket Srinivasan Justin Hoey

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 Atmospheric Pressure Chemical Vapor Deposition of Silicon
thin films using cyclohexasilane
Srinivasan Guruvenket, Justin Hoey, Kenneth Anderson, Matt Frohlich, Gregory Strommen,
Robert Sailer and Philip Boudjouk

Centre for Nanoscale Science and Engineering, North Dakota State University

1805, Research Park Drive, Fargo, ND, 58102, USA

Abstract: We report the deposition of silicon thin films at high chemical vapor deposition at ambient pressure. Detailed
rates using atmospheric pressure chemical vapor deposition (AP­ analysis on growth rates and properties of the thin films were
CVD) with cyclohexasilane (CHS), a liquid-hydrosilane. A
carried-out to derive the process-properties relation.
precursor solution of CHS in cyclooctane was aerosolized and
subsequently vaporized prior to contacting with the substrate. II. EXPERIMENTAL
Using CHS, Si thin films were obtained at temperatures as low as
300°C. A deposition rate of -SO nmts was observed at 500°C; CHS diluted in cyclooctance (Sigma-Aldrich), is controllably
while good-quality Si films were realized at 400°C. Structural injected using a syringe pump into an ultrasonic horn atomizer
analysis of the films indicates a combination of amorphous and (Sono-Tek Inc. Milton, NY) operating at 120 kHz. Helium
nano-crystalline Si phases, withe 2-3 orders of photoconductivity.
(He) at 50 sccm flows through the atomizer to carry the
aerosol mist to a circular showerhead. An additional 3 LPM of
Index terms: Cyclohexasilane, AP-CVD, Si thin films, high-rate He assist vaporization of the aerosol, which is then delivered
growth, roll-to-roll deposition, high-throughput manufacturing
to the substrate surface. The substrate can be heated to a
and silicon.
maximum of 500°C and the substrate-heater assembly is fixed
to an X- Y stage, allowing for controllable movement beneath
I. INTRODUCTION the showerhead. The entire apparatus (AA-APCVD) is located
inside an inert atmosphere (N2, less than 1 ppm O2) glove box
Si is the preferred material for solar-cell industries because of
to preclude exposure of CHS and the deposited Si thin films to
its environmentally benign, inexpensive, and abundant
ambient oxygen and water. A schematic depiction of the
characteristics. However, the Si thin film industry is currently
process is presented in the Fig.I.
experiencing reduced market competitiveness due primarily to
barriers associated with the thin film manufacturing process,
i.e., plasma enhanced CVD (PECVD), that utilizes monosilane
(SiH4). Inefficient utilization of SiH4 ( � 15%) and poor
deposition rates associated with PECVD make Si thin film
solar cells (Si-TFSC) more expensive than emerging
chalcogenide and chalcopyrite based TFSCs.
.... Carrier gas
The difficult associated in handling pyrophoric silane gaseous
and the substantial potential for reduced processing costs has
catalyzed the development of inventive routes to Si thin films
using alternative Si precursors. Using higher order
hydrosilanes for CVD has proven beneficial by several
authors, but the challenge in vaporization and transportation of
these silanes and their limited availability has constrained
progress. Liquid cyclic hydrosilanes, ,i.e, cyclopentasilane
Shower
(SisHIO) and cyclohexasilane (Si6H1 2), have enabled the
head
realization of Si thin films via solution processing at ambient
pressure although the limitations in scale-up remain Heater
unaddressed.

NDSU's silicon group pioneered the synthesis of high purity

cyclohexasilane and routinely produces 10-15 g scale batches
in our labs. In this article we report the deposition of Si thin Fig. I. Schematic representation of aerosol assisted AP-CVD.
films using NDSU synthesized CHS via an aerosol assisted

978-1-4799-4398-2/14/$31.00 ©2014 IEEE 3068

 Thin film depositions were done on 1" x l" Si02 (quartz) anticipate improvement in precursor efficiency with adequate
°
substrates at 300 - 500 C, while all other parameters, modification to our CVD reactor.
including CHS flow rate, were kept constant. Thickness of the
B. Raman Spectroscopic Analysis
deposited Si thin films was determined using contact profiler
(KLA Tencor). Raman spectroscopic analysis were performed Films deposited at various substrate temperatures were
using HORIBA Jobin Yvon LabRAM ARAMIS confocal characterized using Raman Spectroscopy to determine micro­
imaging system with a 532 nm Nd:YAG laser source. Electrical structure. Fig. 3 shows the Raman spectra of the films deposited
properties of these films were measured with an Agilent B1500A at different substrate temperatures. Film deposited at 300 °C
semiconductor analyzer under AM l.5 G illumination and in the exhibit broad band between 475 -500 cm-I which is due to
dark inside a grounded metal shell. transverse-optical (TO) phonon mode arising from a-Si. Similar
trend was observed for Si thin film deposited at 250°C (not
shown in the figure). As the substrate temperature increased the
II. RESULTS AND DISCUSSION band position shifts to higher wave numbers indicating possible
ordering in the structure along with the contribution from the a-Si
A. Growth Rate Analysis
phase. The presence of a broad band between 490 to 500 cm-I
Post-deposition, growth rates were determined at different indicate the existence of intermediate or mixed phases (arising
temperatures by dividing film thickness by time (Fig. 2). For from grain boundaries, defects and ordered small crystallites in
comparison, the growth rate of Si thin films obtained using amorphous Si phases) for the films deposited at 350°C and
23
SiH4 (APCVD, from the literature) is provided. , Activation above. The intermediate phase consists of a-Si and nc-Si; while
energies (Ea) of the Si thin films were obtained using standard the small band that appears between 500 and 510 cm,l is
methods and determined to be 0.3 eV for CHS, which is � 5-8 characteristics of nc-Si phase (ordered c-Si peak appears at 52l.5

times lower than SiH4 (Ea: l.6-2.5 eV). cm,I). At the deposition temperatures of 400 and 450°C the
contribution from mixed phase and nc-Si increases depicting
100
higher concentration of nc-Si in the film, while for the Si film
deposited at 500°C shows a downward shift in the band position
depicting the presence a-Si:H phase.
:0-
c
0
u nc-Si:H
OJ 10
'"
E c-Si
.s (b)
500°C
2
�
.r:
� AA-APCVD
e
<.!)

(Eversteyne, 1974)

0.1 +---�-�-�-r--��-r--r-��-,-��-I
200 400 600 800 1000

Temperature te)
Fig.2. Growth rate of Si thin film obtained using CHS and SiH4 at
atmospheric pressure.

° 200 250 300 350 400 450 500 550 600

CHS show substantial film formation at 300 C, while SiH4
17
shows no significant film formation at these conditions.
45
Kanoh , used a low-pressure CVD process to deposit Si thin
films from tri and tetra-silanes and observed film formation at
° 6
substrate temperatures as low as 300 C. Ellis used APCVD
with a mixture of di-, tri-, and tetrasilanes to deposit Si thin
6
films and achieved a deposition rate of 8.5 nrn/s at 525°C. In
our investigation, a phenomenal growth rate of 50 nrn/s
°
using CHS at 500 C (at atmospheric pressure) is observed,
which is � 30x higher than growth rates obtained using
tetrasilane and � 6x higher than with mixed oligosilanes. To
the best of our knowledge, this is the highest Si deposition rate
obtained using thermal CVD (without plasma assistance).
Preliminary analysis shows a 40% utilization of Si 6HI2 at 400
°
C, which is higher than well-established PECVD routes. We
Wavenumber (cm-1)
Fig.3. Raman spectra of Si thin films deposited from CHS using
aerosol assisted AP-CVD.
C. Electrical Properties ofSi thin films
Conductivity of Si thin films deposited with CHS at different
� temperatures is presented in Fig.4. AP-CVD experiments using
CHS produced near device quality intrinsic silicon films with at
350 and 400°C dark conductivity of 10-11 to 10,10 S/cm and, a
light conductivity value of 10,8 S/cm (photosensitivity of 102_104)
without hydrogen dilution during deposition. Photosensitivity
5
factors 2: 10 represent a photovoltaic quality Si film with dark
11 5
and light conductivities of 10- and 10- S/cm, respectively,
indicate an absence of electrically active defects and a low
3 19
recombination of charge carriers in the film. , The electrical

978-1-4799-4398-2/14/$31.00 ©2014 IEEE 3069

 TABLE 1
PROPERTIES OF SI THIN FILMS OBTAINED USING CHS via AA-APCVD, SPIN COATING AND A COMPARISON WITH LPCVD AND
PECVD USING SiH4•

AA-APCVD w CHS* LPCVD w/ SiH4 (lit) PECVD w/ SiH4 (lit)

Growth rate Up to 50 nmlsec 0.01 to 1 nmlsec 1-5 nm/sec

Pressure Atmospheric Medium vacuum Medium vacuum
Precursors Soluble solids/liquids Hazardous gases Hazardous gases
Temperature 300-500+°C 500-1000°C 25-450°C
3 4 2 7 3 6
Photosensitivity 10 _10 (a-Si:H) 10 _10 (a-Si:H, c-Si) 10 _10 (a-Si:H)
1
Si dep. efficiency �40% �up to 100% �15%
*unoptimized
properties of Si thin films obtained from CHS using AP-CVD continuous roll-to-roll deposition of Si-TFSCs at
indicate the possibility of electrically active defects. ambient pressure.

10.7
Q

I
• Dark IV. ACKNOWLEDGEMENT
0 AM 1.5G
Financial support from the Department of Energy (Grant DE­
0 0
10'"
0 FC36-08G088160) is gratefully acknowledged.
E
u

� 0 REFERENCES
10.11 •
:::-
'> [1] M. A. Kreiger, D. R. Shonnard, J. M. Pearce, "Life cycle
n analysis of silane recycling in amorphous silicon-based solar
�

Resour. Conserv. Recy.,

u
c • photovoltaic manufacturing", vol. 70,
0 '0
() 10·
•
• pp 44-49,2013.

[2] F. C. Everstey, "Chemical-Reaction Engineering in

Semiconductor Industry", Philips Res. Rep., vol. 29, pp 45-66,
10'"
1974.
300 350 400 450 500

Substrate temperature (0C) [3] M. L. Hammond, Hand book ofthinjilm deposition, Editor: K.
Seshan,Elsevier, 2012.
Fig.4. Dark and Light conductivity of Si thin films deposited using
CHS via aerosol assisted AP-CVD. [4] H. Kanoh, O. Sugiura, P. A. Breddels, M. Matsumura,
"Optimization of Chemical Vapor-Deposition Conditions of
A brief summary of the key results obtained using AA­ Amorphous-Silicon Films for Thin-Film Transistor
APCVD in comparison with conventional technologies Application",Jpn J Appl Phys 1,29,2358 1990.
is presented in Table 1.
[5] H. Kanoh, O. Sugiura, M. Matsumura, "Chemical-Vapor­
Deposition of Amorphous-Silicon Using Tetrasilane", Jpn. 1.
III. CONCLUSIONS
Appl. Phys., 1,32,2613-2619,1993.
We deposited Si thin films using CHS and observed
deposition rates of �50 nm/s. Micro-structure of the Si [6] F. B. Ellis, R. G. Gordon, "Simple Method for Preparing

thin films (a-Si:H and nc-Si:H) are akin to Si thin films Hydrogenated Amorphous-Silicon Films by Chemical Vapor­
Deposition at Atmospheric-Pressure", J Appl. Phys., 54, 5381-
obtained via PECVD using SiH4• Near device quality (2-
5384,1983.
3 order photoconductivity) Si thin films were obtained.
This new process to deposit Si thin films using CHS at
very high deposition rates that is amenable for scale-up
can potentially help in realizing, an inexpensive

978-1-4799-4398-2/14/$31.00 ©2014 IEEE 3070

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