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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 47, NO. 1, JANUARY 2000

Study and Fabrication of PIN Photodiode by Using

ZnSe/PS/Si Structure
Chung C. Chang, Member, IEEE, and Ching H. Lee

AbstractIn this experiment, the PIN photodiode by using

ZnSe/porous Si/Si structure was investigated. The single crystal
ZnSe epilayer is successfully grown on porous silicon substrate
with CVD system. Indium is as a dopant to reduce the resistivity of
ZnSe intrinsic layer. To control the different thickness of n ZnSe
layer will change the photocurrent and responsivity of the ZnSe
PIN diode. The best diffusion conditions are diffusion temperature
of 300 C and driving time of 30 min. The responsivity of device is
0.03 A/W. In addition, the dark current of the photodiode is near
zero.
Index TermsPhotocurrent, photodiode, porous silicon, responsivity, ZnSe epilayer.

I. INTRODUCTION

N 1958, Uhlir and Turner [1] found that bulk silicon

could be transformed through anodization in hydrofluoric
acid into porous silicon (PS), a material extensively ridden
with pores. One of its major applications was silicon-on-insulator (SOI) technology [2] in which active microelectronic
devices were dielectrically isolated by the oxidation of the
underlying porous silicon. A more recent application is the
fabrication of Si-based optoelectronic devices [3], [4]. Although the exact source of luminescence remains unclear,
there are three explanations of the light emission mechanism
[5]: 1) Energy gap quantization from quantum-sized silicon
(Si) crystals in porous silicon [5]; 2) wide energy gap surface
silicon complexities, including siloxane [6], Si oxide and Si
hybrides; and 3) hydrogenated amorphous silicon formed on
the surface regions of porous silicon [7].
Another related aspect of growing importance are the wide
energy gap II to IV compounds from research on blue-green
optoelectronic devices [8]. Since the energy gap of ZnSe at
room temperature is 2.68 eV, which approaches the region of
blue light, research in this area is becoming quite interesting. A
ZnSe epilayer on a GaAs substrate in a photoelectronic device
can be utilized as a short wavelength video digital disk (DVD)
pickup head that enables larger data storage capacities. However, the cost of GaAs substrates is still higher than that of Si
substrates. Although ZnSe epilayers can be grown on Si substrates for optoelectronic devices at lower cost and for greater
number of potential applications, the process is difficult when
utilizing a conventional, inexpensive chemical vapor deposition
Manuscript received May 3, 1999. The review of this paper was arranged by
Editor P. K. Bhattacharya.
The authors are with the Department of Electrical Engineering, National
Taiwan Ocean University, Keelung, Taiwan, R.O.C. (e-mail: ccchang@ind.ntou.edu.tw).
Publisher Item Identifier S 0018-9383(00)00649-3.

Fig. 1.

Schematic of anodic reaction cell.

(CVD) system due to the sizable lattice mismatch (~4%) between ZnSe and Si. Described in this paper are experiments
involving the growth of ZnSe hetero-epilayers on porous silicon substrates utilizing straightforward CVD techniques, with
the porous silicon buffer layer formed before the deposition of
the ZnSe layer. Successful results included the production of
nearly single-crystal ZnSe epilayers using a simple, low cost
CVD system and the fabrication of ZnSe/PS/Si PIN photodiodes
from this ZnSe film. Also discussed in this paper are PIN photodetector characteristics. For example, since ZnSe/PS/Si PIN
photodiodes have an enhanced blue-violet or even shorter wavelength sensitivity for optical detection systems because of the
2.68 eV energy gap of ZnSe, these can serve as next-generation
photodiodes (of blue-violet and shorter wavelengths) for digital
video systems.
II. EXPERIMENTAL PROCEDURE
The silicon wafers utilized in this experiment were mirror- -cm) substrate. Referring to Fig. 1,
surfaced p (111) (
the wafers were placed in Teflon holders and connected to the
anode of a current source, with Pt connected to the cathode.
The wafer was porousized by electrochemical etching in a solution of HF : C2H5OH (at a ratio of 3 : 2 by volume) for 30 s and

00189383/00$10.00 2000 IEEE

CHANG AND LEE: STUDY AND FABRICATION OF PIN PHOTODIODE

51

Fig. 4.

SEM image of device.

Fig. 5.

I V measurement circuits of the devices.

Fig. 2. Fabrication process of photodiode.

photodiodes (as indicated in Fig. 2) were fabricated using photolithography and electrochemical technology, and the photo response of the finished devices were measured under an incandescent tungsten lamp.
III. RESULTS AND DISCUSSION

Fig. 3.

XRD pattern of ZnSe single crystal thin film.

the current density of anodization was 30 mA/cm2. Following

anodization, a 0.4 m ZnSe thin film was deposited onto the
porous silicon substrate utilizing CVD techniques. Indium was
used in this experiment as an N-dopant to lower the high resistivity of the ZnSe thin film to a level that would allow device
fabrication. The dopant was diffused gradually into the ZnSe
epilayer in N2, which enabled sufficient control over diffusion
conditions to obtain a moderate n-layer thickness. Then, PIN

Fig. 3 is the XRD pattern of the ZnSe epilayers on the porous

silicon and shows the nearly single-crystal formation successfully grown on the Si substrate.
Having a carrier concentration of approximately 10 cm ,
the resistivity of the ZnSe epilayers was too high for device fabrication. Therefore, indium was selected as an ZnSe N-dopant
in this experiment. First, the indium was evaporated at the ZnSe
epilayers and driven into epilayer via an N2 gas medium, which
resulted in the construction of an n+ ZnSe film layer of lower
resistivity. In this experiment, the diffusion temperature was set
at a constant 300 C and the driving time of dopant was varied
to obtain an assortment of doping profiles to produce ZnSe epilayers having differing device characteristics.
Fig. 4 is an SEM surface image of the PIN photodiode devices. Fig. 5 is the currentvoltage ( ) curve measurements

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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 47, NO. 1, JANUARY 2000

(a)

(b)

Fig. 6. (a) The I V characteristic of device for indium driving time

Fig. 7. I V characteristic of ohmic contact driving time

= 10 min and (b) The I V characteristic of device for indium for driving time = 120 min.

= 30 min.

from the circuits of the devices. Fig. 6(a) indicates the

characteristics of the ZnSe(n)/ZnSe(n)/PS/Si(p) PIN diode devices as measured with a Tektronic 752 when the driving time of
dopant was 10 min. As indicated in Fig. 6(a), 10 min of driving
time was not sufficient to excite the devices, which required a
minimum of 30 min. Fig. 6(b) is the characteristics of devices having a driving time of 120 min and shows the appearance of p-n junctions characteristics. Fig. 7 is the characteristics of an ZnSe epilayer under the same conditions, but on an
-cm); demonstrating that ohmic
n (111) substrate (
contacts are obtainable when the indium driving time was 30
min at a diffusion temperature of 300 C. Fig. 8 is the relationship between the cut-in voltage (defined as the voltage at 0.1 mA
forward current) and the driving time, which illustrates that the
cut-in voltage decreases as the driving time increases; since the
width an n ZnSe layer decreases when the indium driving time
is increased, it follows that the cut-in voltage decreases with increases in driving time.
Fig. 9(a)(d) are the characteristics of devices with
driving times of 30, 60, 90, and 120 min, respectively, under
illuminated conditions. Fig. 9 indicates that the photocurrent
increases as the intensity of incident light become greater
because the multiplication of electron-hole pairs is a produced
by light excitation in a direct relationship to the degree of

Fig. 8.

Relationship between cut-in voltage and driving time.

intensity. Fig. 10 shows that a sample having a driving time

of 30 min produced a higher photocurrent under the same
intensity of incident light, but the photocurrent decreased when
the driving time was increased; since the thickness of both
the n ZnSe layer and the depletion layer decreased when the
driving time was increased, the number of electron-hole pairs
produced by illuminating the depletion layer also decreased,
and the photocurrents of samples increased as the intensity of
incident light was increased. Fig. 11 shows the relationship
between responsivity and incident light intensity at different
driving times and indicates that a devices having a driving time
of 30 min exhibits better responsivity at a given intensity of
incident light, with the responsivity decreasing proportionately
as the incident light intensity was increased. The photovoltaic
effect may be the main reason to decreasing the responsivity
since the higher light intensity reduce depletion layer width
At an indium doping diffusion temperature of 300 C and

CHANG AND LEE: STUDY AND FABRICATION OF PIN PHOTODIODE

53

(a)

(b)

(c)

(d)

Fig. 9. (a) I V characteristic of device (driving time 30 min) under light illuminated. (b) The I V characteristic of device (driving time 60 min) under
light illuminated. (c) I V characteristic of device (driving time 90 min) under light illuminated. (d) The I V characteristic of device (driving time 120 min)
under light illuminated.

driving time of 30 min, the best responsiveness measured in

this experiment was 0.03 A/W.
IV. CONCLUSION
In summary, n-ZnSe/PS Si/p-Si structures were successfully
utilized for the fabrication of the PIN diodes, with indium selected an N-type dopant to reduce the intrinsic high resistivity
of the ZnSe epilayers. Since the thickness of the n layer could
be controlled by changing the driven diffusion conditions of the
indium, ZnSe PIN diodes of varying photocurrent and responsiveness characteristics were produced. The highest PIN diode
responsiveness encountered was 0.03 A/W, which was obtained
at an indium dopant diffusion temperature of 300 C and driving
time of 30 min; furthermore, the dark current of this particular
ZnSe/PS/Si PIN diode was close to zero due to the excellent
quality of the ZnSe epilayer. Since a nearly single-crystal ZnSe
epilayer could be produced on PS/Si substrate with inexpensive,
simple CVD systems for the fabrication of short wavelength
ZnSe/PS/Si PIN photodetectors, such components can be made
available at lower cost. Moreover, the response of ZnSe/PS/Si
short wavelength diodes for photodetector applications will be
enhanced as porous silicon quality is improved.

Fig. 10. Relationship between photocurrent and the intensity of incident light
for different driving times.

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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 47, NO. 1, JANUARY 2000

[4] P. Steiner, F. Kozlowski, and W. Lang, Blue and green electroluminuscence from a porous silicon device, IEEE Electron Devices Lett., vol.
14, no. 7, p. 317, 1993.
[5] T. Matsuda and K. Tanino, Two-dimensional intensity distribution of
photoluminescence from porous silicon, J. Appl. Phys., vol. 80, no. 3,
p. 1743, 1996.
[6] M. S. Brandt, H. D. Fuchs, M. Stutzmann, J. Weber, and M. Cardona,
The origin of visible luminescence from porous silicon: A new interpretation, Solid State Commun., vol. 81, p. 307, 1992.
[7] R. W. Fathauer, T. George, A. Ksendzov, and R. P. Vasquez, Visible
luminescence from silicon wafers subjected to stain etches, Appl. Phys.
Lett., vol. 60, p. 995, 1992.
[8] M. Yamaguchi, A. Yamamoto, and M. Kondo, Blue luminescence from
ZnSe diodes, J. Appl. Phys., vol. 48, p. 196, 1977.

Fig. 11. Relationship between responsivity and the intensity of incident light
for different driving times.

REFERENCES
[1] D. R. Turner, Electropolishing silicon in hydrofluoric, J. Electrochem.
Soc., vol. 105, pp. 402408, 1958.
[2] G. Bomchil, A. Halimaoui, and R. Herino, Porous silicon: The material
and its applications to SOI technologies, Microelectron. Eng., vol. 8, p.
293, 1988.
[3] L. T. Canham, Silicon quantum wire array fabrication by electrochemical and chemical dissolution of wafers, Appl. Phys. Lett., vol. 57, p.
1046, 1990.

Chung C. Chang (M88) was born in Taiwan,

R.O.C., on January 9, 1957. He received the B.S.,
M.S., and Ph.D. degrees in electrical engineering
from the National Cheng Kung University, Taiwan,
in 1979, 1981 and 1989, respectively.
In 1989, he joined the National Taiwan Ocean
University, Keelung, as Associate Professor in the
Department of Electrical Engineering. He had been
the Chairman of the department from 1992 to 1995.
Currently, he is a Professor in the department. He
is working on sensors, semiconductor devices, IC
process, photoelectronic devices, and microelectromechanical system.

Ching H. Lee was born in Taiwan, R.O.C., on February 21, 1973. He received the B.S. and M.S. degrees
from the Department of Electrical Engineering, National Taiwan Ocean University, Keelung, Taiwan, in
1995 and 1997, respectively.
He is now engaged in IC processes at Winbond
Electronics Corporation, Taiwan.