IEEE PHOTONICS TECHNOLOGY LETTERS, VOL. 16, NO.

8, AUGUST 2015 1927

Thin Film Silicon Nanoparticle UV Photodetector

O. M. Nayfeh, S. Rao, A. Smith, J. Therrien, and M. H. Nayfeh

AbstractWe constructed ultraviolet (UV) photodetectors by

room-temperature deposition of Si nanoparticle films on Si p-
type substrates. Silicon nanoparticles of 1-nm diameter are
dispersed from Si wafers using electrochemical etching. The
currentvoltage characteristics indicate a photoconductor in
series with a diode-like junction with a large enhancement in the
forward current under UV illumination. With increasing
wavelength, the response drops rapidly, dropping to a few
percent at 560 nm. These results point to a sensitive UV detector
with good visible blindness where the particle films effectively
constitutes a wide-bandgap material.
Index TermsNanotechnology, photoconducting devices, pho- Fig. 1. Schematic of the silicon nanoparticles UV photodiode.
toconductivity, photodetector, photodiode, semiconductor devices, silicon, thin films.

T HERE HAS been great interest in emitters, sensors, or

filters that are efficient and compatible with the existing
silicon-based integrated circuit technology [1][8]. Silicon,
the most common semiconductor, has an indirect bandgap of
1.1 eV, corresponding to an infrared wavelength of 1.1 m,
making it not useful for ultraviolet (UV) detection. Thus, none
of the material available for UV detection so far is based on
elemental silicon. We present here UV photodetectors with
superior efficiency created by deposition of Si nanoparticle
films on Si substrates. Contrary to bulk Si, Si nanoparticles
exhibit behavior of direct wide-bandgap materials. This makes
it very sensitive to UV light and transparent to visible light,
with good rejection ratio.
Recent research has shown that reducing the size of a Si crystal
to a few tens of atoms ( 1 nm) effectively creates a di-rect
wide-bandgap material [9], [10]. UV light couples to the particles
efficiently to produce electron-hole pairs. Contrary to bulk Si or
large particles, the electron hole pairs do not appre-ciably
recombine via nonradiative processes, allowing charge separation
and collection. Nonradiative recombination is not strong in ultra-
small Si nanoparticles due to strong quantum confinement [11].
This is evidenced by the strong and fast ra-diative recombination
they exhibit. For instance, the emission proceeds over 110-ns
time scale typical of a direct-gap mate-rial with brightness that
exceeds that of common dyes [12][15],
[6]. In this letter, we describe the fabrication of UV
photodetec-tors using the new Si nanoparticle material.
Manuscript received December 12, 2003; revised April 21, 2004. This work
was supported by the U.S. NSF under Grant BES-0118053, by the State of
Illi-nois under Grant IDCCA 00-49106, by the U.S. DOE under Grant
DEFG02-ER9645439, by the NIH under Grant RR03155, and by the
University of Illi-nois at Urbana-Champaign.
O. M. Nayfeh is with the Electrical Engineering Department,
Massachusetts Institute of Technology, Cambridge, MA 02139-4307 USA.
S. Rao, A. Smith, J. Therrien, and M. H. Nayfeh are with the Department of
Physics, University of Illinois at Urbana-Champaign, Urbana, IL 61801 USA
(e-mail: m-nayfeh@uiuc.edu).
Digital Object Identifier 10.1109/LPT.2004.831271
Fig. 2. IV characteristics of a typical diode (a) taken under dark conditions,
(b) taken with 365-nm light from a mercury lamp directed onto the sample, and
(c) the difference of the responses (a) and (b).
We electrochemically dispersed crystalline Si in the mixture
HFH O [12][16]. We prepared blue luminescent 1-nm
particles, which were characterized by electron microscopy and
fluorescent spectroscopy [17], [18]. We start with a p-type
device-quality (100) Si wafer of 48 cm conductivity
( dopant/cm ). An oxide layer of 500 nm is grown on the
substrate. A single pattern or an array of patterns is etched using
HFNH F. We immerse the wafer, positively biased relative to a
platinum electrode, in a suspension of particles in alcohol. A
current is established, depositing nanoparticles in the hole,
producing a film of 500 nm thick with an active region of 5 mm
in diameter. Semitransparent gold of 4-nm thickness is deposited
on the particle film. The 300-nm-thick gold pads are deposited on
the gold layer and on the back of the substrate, providing means
to bias the device, as shown in Fig. 1.
We used a Hg lamp of a fluorescence microscope at powers of
13 mW focused to a spot 2 mm in diameter. Fig. 2(a) shows the
currentvoltage ( ) curves under dark conditions. They show
somewhat rectifying behavior. Similar behavior was observed in
silicon nanoparticle-based devices of equivalent configuration
constructed to conduct electroluminescence studies [19]. The

1041-1135/04$20.00 2015 IEEE

1928
Fig. 3. Response (in arbitrary units) versus wavelength.
forward current, beginning to rise at 0.75 V, increases nonlin-
early and saturates locally to 0.075 mA at 2 V. Beyond 2 V, the
current rises linearly to 0.4 mA at 9 V, with an impedance of 21 k
. At 2 V, the ratio of forward to reverse current is seven. Fig.
2(b) was taken with 2 mW at 365 nm. It shows very strong
rectification. The forward current is enhanced by a factor of 20,
while the reverse current is essentially unaffected. The ratio of
forward to reverse current at 2 V is now 160. Fig. 2(c) gives the
difference of the responses taken with and without 365-nm light.
The spectral responsitivity is the product of the quantum
efficiency for carrier generation and that of charge collection. The
nonlinearity in the response reflect space charge ef-fects,
including multiplication (gain) and saturation, under high charge
densities and fields ( 40 kV/cm). At 1 V, the sensitivity is 150
mA/W. With voltage, it rises to a local maximum of
750 mA/W at 2 V. We use , where is the
wavelength of the incident radiation, is Plancks constant, is
the electronic charge, is the light speed, is the quantum effi-
ciency, and is the gain. For A/W, this gives a gain
of 2.6 at 365 nm, assuming . Other devices tested showed
wider saturation regions (plateau), with softer rises. Responsiv-
ities ranging from 80 to 180 mA/W at 1 V, and 350750 at 2 V
have been measured for different depositions. The device has
good visible blindness. The responsitivity, measured using Hg or
Xe lamps (shown in Fig. 3), drops to 0.036 at 560 nm com-pared
to 22 at 250 nm. Due to propagation problems of deep UV, the
gain at 200 is underestimated.
The dark current is due to leakage from imperfections and
cracks in the film. If the device operates as a shot-limited de-
tector with response time of 0.3 s ( MHz device band-
width), and a leakage current of mA, the signal-to-
noise ratio of the shot noise SNR , where is the
electronic charge is ensured at a level of ( 69 dB). We
should note that no temperature studies have been conducted to
determine the contribution of the thermal (Johnson) noise to the
dark current. Moreover, we made no measurements to control the
dark current using mesoscopic patterning.
We now discuss the response in terms of the films electronic
and physical properties. First, the open circuit impedance is a
few . The high impedance of the film is a direct result of
the fact that the individual nanoparticles, under low doping,
are essentially nonconducting. Under doping of /cm
(48- cm conductivity) as in this sample, less than one in a
million of the 1-nm particles contain one dopant atom,
IEEE PHOTONICS TECHNOLOGY LETTERS, VOL. 16, NO. 8, AUGUST 2015
Fig. 4. IV characteristics of a single 1-nm particles on p-type substrate
recorded by a scanning tunnelling microscope whose tip is above the particle.
hence, there are no unoccupied levels. The high impedence also
indicates a film with negligible cracking, and consistent with the
measured low leakage current ( 0.075 mA). The film, therefore,
acts as a good insulator in the dark, but becomes capable of
conducting electric current when exposed to light. We believe
that conduction is based on hole states generated by the UV
radiation. We examined the mechanism using scanning tunnelling
spectroscopy. We placed a low coverage of 1-nm nanoparticles on
a Si substrate. The room-temperature spectrum, taken using
electron injection from the microscope tip, shows that UV
enhances the transport at a period of 1.0 eV, as shown in Fig. 4.
The period is consistent with carrier confinement energy levels
[16]. If a hole is generated in each particle, and for a closely
packed film, this would correspond to a very high electronhole
density, corresponding
to an effective doping of /cm .
In the device, the nanoparticle film/p-Si substrate represents
the diode-like behavior [19], [20]. The marginal rectification in
the dark (a factor of seven) is related to the fact that the effec-tive
doping of the particle film is very low, with very little con-
duction electrons present. The enhancement in the rectification
upon irradiation (to a factor of 160) is caused by the creation of
the above high electronhole or effective doping density.
The gain (2.6) and spectral responsitivity (750 mA/W) are
related among other factors to the uniformity of the particles (1
nm in diameter). Size uniformity provides uniform confine-ment
energies and bandgaps (3.6 eV). Uniform bandgaps allow
resonant tunnelling between particles, which is much faster than
nonresonant processes. Resonant tunnelling-limited trans-port
provides higher carrier mobility , hence, shorter transit
time according to (assuming a single electron-hole
mobility), where is the applied bias, is the film thickness, and
is the effective mobility [20]. This is to be contrasted with the
laser ablation or chemical vapor deposition (CVD), which
produce a wide size distribution, hence, a wide bandgap distri-
bution. In this case, the conduction proceeds via complicated
paths in search of the same size particles, resulting in longer
paths, hence lower mobility. For instance, the effective mobility
across films of nanoparticles prepared by pulsed laser ablation
was measured to be of the order of cm /Vs [20]. On the
NAYFEH et al.: THIN FILM SILICON NANOPARTICLE UV PHOTODETECTOR
biasing voltage. The same architecture may be used as a light
emitter, or a UV filter for monitoring enzyme reactions. High
efficiency allows the study of extremely small samples, assays
in small volumes, and sensor array for high-speed screening.
Fig. 5. Bandgap versus the lattice constant of materials used in UV detection.
other hand, under the resonant conditions in the present devices,
we expect an effective mobility as large as cm /Vs.
The enhanced responsitivity and gain are also related to the
quality of particle packing. Unlike laser ablation or CVD de-
position, which provides no direct control on the size and the
degree of packing, we utilize uniform particles in close packing
arrangement. In this case, there is minimum non-Si material be-
tween particles that may lead to strong barriers. In our samples,
we expect barriers of 1 nm, thus tunnelling is the dominant
factor. Since the gain is inversely proportional to the transit time,
the reduction of potential barriers enhances the gain and respon-
sitivity [19]. In addition to packing effects, the sensitivity is de-
pendent on the thickness of the film. It must be thin enough to
allow penetration of the radiation, such that a path for carriers is
created across the film. Thicknesses as low 100 nm can be used.
Although more susceptible to nonuniformity and cracks, which
cause leakage, thin films allow usage of larger active areas, and
provide higher gain. For weak radiation or/and thick films, fo-
cusing the radiation may lead to better sensitivity.
Current UV technology utilizes wide-bandgap materials, as
shown in Fig. 5 [5]. These include metal zinc oxide and mag-
nesium zinc oxide, IIIV materials as well as Schottky-type TiO
UV photodiodes. The distinctive aspect of IIInitrides is that their
bandgap are tuneable within the ultraviolet range. Other novel
approaches include organics and phosphors. Sil-icon-based
detection utilizes silicon carbide material [6] and amorphous
silicon alloys [7], [8]. The many UV detectors that revolve
around nitride-based heterostructures are grown on incompatible
substances. Si nanoparticle-based devices may offer an
opportunity for integration on Si. Moreover, the measured
responsitivity is nearly an order of magnitude improvement over
some commercial thin film detectors, and is an improvement over
the sensitivities of 175 and 90 mA/W recently measured in SiC
[6] and in amorphous Si, respectively.
In conclusion, we demonstrated UV photodetectors based on
Si nanoparticle thin film. It provides high sensitivity under low
1929
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