Thin Solid Films 511 – 512 (2006) 654 – 662

www.elsevier.com/locate/tsf

Silicon nanostructures for third generation photovoltaic solar cells

Gavin Conibeer a,*, Martin Green a, Richard Corkish a, Young Cho a, Eun-Chel Cho b,
Chu-Wei Jiang a, Thipwan Fangsuwannarak a, Edwin Pink a, Yidan Huang a, Tom Puzzer a,
Thorsten Trupke a, Bryce Richards c, Avi Shalav a, Kuo-lung Lin d
a
Centre of Excellence for Advanced Silicon Photovoltaics and Photonics, University of New South Wales, UNSW Sydney, NSW 2052, Australia
b
Corporate R&D Center Samsung SDI Co., Ltd. 428-5 Gong-se-ri, Giheung-eup, Youngin-Si, Gyeonggi-do 449-577, Korea
c
Centre for Sustainable Energy Systems, Australian National University, Canberra, ACT 0200, Australia
d
Origin Energy, Adelaide, SA, Australia
Available online 20 January 2006

Abstract

The concept of third generation photovoltaics is to significantly increase device efficiencies whilst still using thin film processes and abundant
non-toxic materials. This can be achieved by circumventing the Shockley – Queisser limit for single band gap devices, using multiple energy
threshold approaches.
At the University of NSW, as part of our work on Third Generation devices, we are using the energy confinement of silicon based quantum dot
nanostructures to engineer wide band gap materials to be used as upper cell elements in Si based tandem cells. HRTEM data shows Si nanocrystal
formation in oxide and nitride matrixes with a controlled nanocrystal size, grown by layered reactive sputtering and layered PECVD. Photoluminescence
evidence for quantum confinement in the Si quantum dots in oxide agrees with the calculated increase in PL energy with reduction in dot size. Resistivity
measurements with temperature give tentative proof of conduction and we are investigating junction formation in these materials.
We are also using similar Si quantum dot structures in double barrier resonant tunneling structures for use in hot carrier solar cell contacts.
These must collect carriers over a limited energy range. Negative differential resistance has been observed in room temperature I – V on these
samples, a necessary proof of concept for selective energy filter contacts.
D 2006 Elsevier B.V. All rights reserved.

Keywords: Nanostructure; Photovoltaic; Third generation

1. Introduction implementation of photovoltaics. The twin effects of increased

In parallel with the current boom in first generation wafer
based photovoltaic technologies and the rise of second
generation thin film approaches that have the potential to
reduce material and deposition costs, research is proceeding
on future technologies. These approaches, termed ‘‘third
generation,’’ aim to reduce the cost (per Watt peak) of ‘‘thin
film’’ second generation technologies by increasing the
efficiency of the photovoltaic devices with only a small
increase in areal costs [1]. Also, in common with the silicon
based second generation thin film technologies, these will use
abundant and non-toxic materials. Thus, these ‘‘third gener-
ation’’ technologies will be compatible with large scale
* Corresponding author. Tel.: +61 2 93857858; fax: +61 2 93855412.
E-mail address: g.conibeer@unsw.edu.au (G. Conibeer).
0040-6090/$ - see front matter D 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.12.119
efficiency and low cost thin film processes has the potential to
reduce costs per peak Watt of generating capacity very
significantly, perhaps by more than a factor of 10 to less than
0.20/Wp [1].
To achieve such efficiency improvements the Shockley–
Queisser limit for single band gap materials must be
circumvented. This requires multiple energy threshold devices
such as the tandem or multi-colour solar cell. We are
investigating a number of approaches based on nanostructures
to achieve such multiple energy threshold devices [1,2].
2. Third generation approaches
The two most important power loss mechanisms in single-
bandgap cells are the inability to absorb photons with energy
less than the bandgap (1 in Fig. 1), and thermalisation of
photon energy exceeding the bandgap, (2 in Fig. 1). There have
 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662
Energy
2
3 Tandem cells are stacks of individual cells with different
4
5 spectrum, usually connected together in series. We aim to
qV
5 The main challenge for a nanostructure engineered material
4
1 for a tandem cell is to achieve sufficient carrier mobility and
2
Fig. 1. Loss processes in a standard solar cell: (1) non-absorption of below band
gap photons; (2) lattice thermalisation loss; (3) and (4) junction and contact
voltage losses; (5) recombination loss.
been proposed three families of approaches for tackling them
[2]: (a) increasing the number of bandgaps; (b) capturing
carriers before thermalisation; and (c) multiple carrier pair
generation per high energy photon or single carrier pair
generation with multiple low energy photons. Of these, tandem
cells, an implementation of strategy (a), are the only ones
which have been realised with efficiencies exceeding the
Shockley –Queisser limit.
There are several nanostructured cell proposals that aim at
higher efficiency than is possible using a single p– n junction.
Among these ideas are quantum well [3], and quantum dot
solar cells and impurity band cells relying on interpenetrating
networks of quantum dots [4], all of which use strategy (a).
However in addition to the more efficient utilization of above
and below band gap photons the Third Generation Strand of the
Centre of Excellence at UNSW aims at approaches that also use
abundant, non-toxic materials (such as silicon) and processes
that are amenable to large scale production (i.e. thin film
processes).
We aim to implement strategy (a) by fabricating a tandem
cell based on silicon and its oxides and nitrides using reduced
dimension silicon nanostructures to engineer the band gap of
an upper cell material. We are also tackling strategy (b) by
investigating the ‘‘Hot Carrier solar cell’’ in which carrier
cooling is slowed such that carriers can be extracted before
thermalisation. This requires both an absorber with slowed
carrier cooling properties and collection of carriers over a
limited range of energies, such that cold carriers in the external
contacts do not cool the hot carriers to be extracted. Finally we
are investigating implementation of strategy (c) either by
down-conversion in a layer on the front of the cell or by
application of an up-converter to the rear of a Si cell. Rare earth
doped phosphors in the up-converter absorb below band gap
photons and up-convert two or more to above band gap
photons which are then incident on the Si cell [5].
3. Implementation of third generation strategies
There are various challenges for implementation of the third
generation strategies mentioned above. We have identified
various mechanisms that can be utilised in nanostructures to
address these challenges.
655
3.1. Silicon based tandem cells
energy thresholds each absorbing a different band of the solar
engineer a new silicon-based material to form a top cell above a
silicon cell, see Fig. 2.
hence a reasonable conductivity. For a nanostructure this
generally requires formation of a true superlattice with overlap
of the wavefunction for adjacent quantum wells or quantum
dots; which in turn requires either close spacing between QWs
or QDs or low barrier height.
Another requirement for a tandem cell element is the
presence of some form of junction for carrier separation. This
can either be a grown or diffused p – n junction or a p –i– n
junction with the superlattice as the i-region. The latter requires
careful control of the workfunctions (and therefore doping) of
the p and n-regions but also means that it is not essential for the
superlattice itself to be doped.
3.2. Hot carrier cells
The concept underlying the hot carrier solar cell is to slow
the rate of photoexcited carrier cooling, caused by phonon
interaction in the lattice, to allow time for the carriers to be
collected whilst they are still at elevated energies (‘‘hot’’), and
thus allowing higher voltages to be achieved from the cell [6].
It thus tackles the major PV loss mechanism of thermalisation
of carriers (loss (2) in Fig. 1 and strategy (b) in Section 2).
Such slowing of carrier cooling only occurs at very high
intensities in bulk semiconductors — for example equivalent to
250 to 2500 suns in reference [7]. However, the reduced
dimensionality in nanostructures offers a promising route for
such a role as they restrict the number of acoustic phonon
modes available because of the Brillouin zone folding that
occurs as a result of the periodicity of the superlattice. Slowed
carrier cooling in QW superlattices has been demonstrated
experimentally [7,8] and is described as an enhancement of the
phonon bottleneck effect. Some of the current authors describe
the likelihood of an increased effect in QD superlattices in [9].
However, this work is principally theoretical at present and is
unlikely to involve Si based nanostructures for some time,
hence it is not considered further here.
Wide bandgap material Silicon quantum dots
(SiO2, Si3N4 or SiC)
Engineered band gap Engineered band gap Silicon cell
upper cell middle cell
Fig. 2. Si based tandem solar cell with one or two upper cells with wider
effective bandgaps made by varying the layer thickness in Si QD superlattices.
656 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662
Selective energy contacts
Electron contact Hot carrier Hole contact
TA TH TA
δE
-
e selective
energy contact Es
Ef(n) Hot carrier
distribution
Δμ A = qV Ef
small Eg
Ef(p)
Es h+ selective
energy contact
Fig. 3. Schematic and band diagram of an ideal hot carrier cell. The absorber
has a hot carrier distribution at temp T H. Carriers cool isoentropically in the
mono-energetic contacts to TA. The difference of the Fermi levels of these two
contacts manifests as a difference in chemical potential of the carriers at each
contact and hence an external voltage, V.
For the hot carrier cell to be effective ‘‘hot’’ carriers, as
described above, must be collected from the absorber over a
very small energy range with selective energy contacts. This is
so that only a small amount of their excess energy above the
band edge is lost in cooling to the contact temperature. In
thermodynamic terms, the carriers are thus collected with a
very small increase in entropy. Ideally this collection would be
isoentropic using mono-energetic contacts, see Fig. 3.
A quantum dot approach offers potential for such contacts
via a double barrier resonant tunneling structure with quantum
dots providing a discrete energy level between two insulating
barriers. This will give conduction strongly peaked at the
discrete energy level [10]. Experimental work is focused on
devices that demonstrate such resonant tunneling effects
without requiring sophisticated epitaxial structures [11,12].
3.3. Up- and down-conversion
We are also interested in nanostrutures for up-conversion of
sub-band gap light normally not absorbed in a PV cell. Recent
work has shown a significant proof of concept for up-
conversion using Er3+ atoms dispersed in a phosphor matrix,
via an energy transfer mechanism. Peak external quantum
efficiencies of over 2.5% have been achieved at a wavelength
of 1523 nm [13]. This has been demonstrated to give a
corresponding increase in the spectral response in the 1480 –
1580 nm wavelength range for a bi-facial Si solar cell [14].
Techniques are being investigated to extend this increase to a
wider range of absorption wavelengths.
Research of efficient down-conversion mechanisms is less
advanced to date, however it is conceptually easy to imagine
the inclusion of a down-converting luminescent species within
the solar cell antireflection coating [1]. Silicon nanostructures
in the form of porous silicon, have however been used for
‘‘down shifting’’ or ‘‘photon cutting’’ [15]. So far, in such
devices an incident photon is shifted in energy to a longer
wavelength with the excess energy lost non-radiatively. This
can have the advantage of tailoring the spectrum for the
particular absorptance with wavelength of a given semicon-
ductor but does not circumvent the Shockley– Queisser limit
and is therefore not strictly third generation. Attempts are
underway [15] to make the energy cutting a radiative transition
and hence true down conversion but as yet this has not been
achieved.
Hence, as neither up- nor true down-conversion approaches
at present use silicon nanostructures, these will not be
discussed further in this paper.
4. Silicon quantum dot nanostructures
The concept is to engineer the band structure of silicon
based materials either for application as wide band gap
materials in a silicon based tandem cell (see Section 3.1) or
for hot carrier cells (see Section 3.2). The engineering takes the
form of fabrication of silicon nanocrystals embedded in either a
SiO2 or Si3N4 matrix. Nanocrystals less than 7 nm in diameter
behave as quantum dots exhibiting quantum confinement. With
such Si quantum dots spaced sufficiently close together,
overlap of the wavefuctions of quantum confined carriers in
adjacent dots can allow the formation of a true superlattice with
the confined states smearing out to form a mini-band. For
sufficiently broad mini-bands this effectively results in a new
semiconductor material with a wider band gap than Si. This in
turn can be used to fabricate wide band gap p– n or p– i– n
junction solar cells that can be used as tandem cell elements on
top of normal Si cells, thus creating an ‘‘all-Si’’ tandem cell
with voltage boosted from that of a normal Si cell.
As reported elsewhere [16,17] such Si quantum dots have
been fabricated by co-sputtering deposition of silicon rich
layers interspersed with stoichiometric SiO2 layers (an appli-
cation of the method of Zacharias et al. [18] to photovoltaics).
On annealing at 1100 -C silicon precipitates from the super-
saturated solid solution to form nanocrystals. For layers of
thickness less than about 4 nm, the precipitation enters a
regime of 2D diffusion in which the dot size is accurately
controlled by the layer thickness.
4.1. Physical characterisation
Direct physical evidence of the crystallinity of these
nanocrystals has been obtained from high resolution TEM
(see Fig. 4a and b), using an electron beam up to 300 keV [16].
Crystal planes are apparent in many of the darker areas in these
HRTEM images. The darker areas are denser material in a less
dense matrix, which are attributed to silicon nanocrystals in a
SiO2 matrix. The fact that crystal planes are not seen in all of
 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662 657

Secondary ion mass spectrometry data have also been

obtained for several of the Si nanostructure samples, which
confirm changes in Si and O concentration on the scale of
down to 2 nm in the growth direction.

4.2. Optical measurements

PL results indicate quantum confined properties as

evidenced by the increase in the photo-luminescent energy in
PL experiments; see Fig. 6.
Fig. 6a shows an increase in PL energy as nanocrystal size
decreases, thus demonstrating quantum confinement and hence
formation of quantum dots. It also shows a dramatic increase in
PL intensity on going from a dot diameter of 4.7 to 3.5 nm.
This correlates well with the greatly increased uniformity in
Si quantum dot size as the deposited layer goes from 4.7 to
3.5 nm, as shown in Fig. 5a on change of diffusion mechanism,
see above. The large increase in PL energy is due to the much
greater signal at a given energy with good dot size uniformity.
(The fact that this intensity drops again is discussed below.) An
increase in PL intensity is also to be expected as dot size

a
9.0

8.0

7.0
Si Dot Size [nm]

6.0

5.0

4.0

Fig. 4. Cross-sectional TEM (a) HRTEM (b) images of Si QDs in oxide. (a) 3.0
shows the layered structure and (b) shows individual nanocrystals in which 2.0
crystal planes can be seen.
1.0

0.0
0 100 200 300 400
the dark areas is thought to be due to the fact that the planes
will only be apparent for orientations that happen to be closely Deposition Time [sec]
aligned to the substrate; with the electron beam also aligned to b
18
the substrate. A study of many such images has not revealed
Number of Quantum dots [a.u.]

any alignment to the substrate within the cross-sectional plane 16

or any preferred orientation for the nanocrystals. Nor would 14

any such preferred orientation be expected, as the model of 12
nanocrystals precipitating from a super-saturated solution
10
should generate random orientation.
The data shown in Fig. 5 are measured from HRTEM 8
images for samples at several deposition times [16]. There is a 6
sharp decrease in the nanocrystal size distribution on reduction
4
in layer thickness from 4.7 to 3.5 nm. This indicates a transition
from a bulk diffusion mechanism of Si atoms during 2
precipitation to a constrained two dimensional diffusion 0
regime, such that the nanocrystal size is defined by the layer 2.5 3.5 4.5 5.5 6.5
thickness. This is an important self regulation effect which Diameter of Si quantum dots [nm]
gives much greater uniformity in nanocrystal opto-electronic Fig. 5. (a) Dependence of quantum dot size distribution on deposition time as
properties, at least in the growth direction, as indicated for measured by HRTEM (other sputtering parameters optimised). (b) QD size
photoluminescence (PL) in Fig. 6, below. distribution for deposition time of 280 s.
658 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662

a ideal bandgap for a 2-cell tandem on bulk silicon but 2 nm QDs

Si nanocrystal size [nm]
PL energy [eV] Integrated PL should be much easier to fabricate than the 1 nm quantum well
intensity [a.u.]
2.0 3.0 3.4 4.6 5.0 required for such a bang gap.
1.80 30000
Referring again to Fig. 6a, the fact that the PL intensity
1.70 25000 decreases again for nanocrystal sizes less than 3.5 nm requires
some discussion. One would expect an increase in PL intensity
1.60 20000 due to localisation as nanocrystal size decreases or for it to
remain constant. However, as the nanocrystal size decreases
1.50 15000
there is a reducing overall volume of crystalline Si, because the
1.40 10000 number of layers is the same in all the samples measured.
Hence, PL absorption and hence total emission also decreases.
1.30 5000 The data in Fig. 6b shows a normalisation for the volume
effect distorting the PL intensity data in Fig. 6a. It shows a
1.20 0
100 150 200 250 300 350 curve normalised to the Si volume for 2 nm dots. The result of
Deposition times [sec] this normalisation is a flatter curve but not one that is constant
b for data below 3.5 nm dot size, as would be expected. This
Photo-luminescence at 15K PL intensity
and normalised data
could be due to two additional effects:
Normalised to volume of 2nm QDs
PL intensity [a.u.]
1. There is an increasing surface area to volume ratio as the
nanocrystals shrink, which increases the chance of recom-
bination of photogenerated pairs at surface states, which
would require a further normalisation to surface area to
volume ratio. (Or more precisely to interfacial volume, i.e.
that containing defects.) However, at present there is an
insufficient number of data points to attempt such a
normalisation.
2. It is assumed that all excess Si in the Si rich oxide
2 2.5 3 3.5 4 4.5 5 5.5 6 precipitates to nanocrystals on annealing. This assumption
QD dia (nm) may become increasingly less valid as dot size decreases.
Fig. 6. (a) PL energy ? and integrated intensity n (15 K) as a function of The annealing time required for complete 2D precipitation is
deposition time, showing quantum confined energy in silicon quantum dots. likely to increase as layer thickness decreases and it is quite
Deposition time is also calibrated for dot diameter by TEM. (b) PL intensity possible that this is not yet long enough for small dots.
data normalised for decreasing volume.
4.3. Electrical measurements
decreases because of the increase in spatial localisation of
electrons and holes that will increase the probability of The small thicknesses relax the requirements on carrier-
recombination. mobility within the films. Carriers transfer between the dots by
The expected increase in PL energy with quantum confine- quantum-mechanical tunnelling, enhanced by resonance effects
ment as dot size decreases can in principle be estimated most that are strongest when dots have periodic spacing. Initial
simply using ‘‘effective mass’’ solutions for electrons confined results of the transport properties within these nanostructured-
in a quantum dot. However work on this is as yet at an early semiconductor materials using temperature-dependent conduc-
stage; the proportions of increases in confined energy level tivity measurements are shown in Fig. 7 [21].
with reducing nanocrystal size are well modelled but calcula- Fig. 7 shows data for a Si QD sample that has been annealed
tion of the actual values requires further development of the and has undergone hydrogenation in a hydrogen plasma.
theory. Other authors have found that other factors are required Before hydrogenation resistivity at room temperature is about
than the simple application of effective mass theory for silicon 105 V cm, after hydrogenation it decreases dramatically to
nanocrystals, such as the effect of oxygen double bonds at the about 200 V cm. This could be due to passivation of traps on
interface between nanocrystals and the matrix, e.g. [19]. the surface or in the bulk of the QDs or to an increase in the
Some of the current authors have demonstrated sufficient number of defects in the oxide allowing transport by hopping.
confinement in a Si quantum well in SiO2 of 1 nm width to More data is required to determine the mechanisms involved.
give a band edge of 1.7 eV (as measured by PL) [20]. For a Resistivity in both cases is seen to increase with decreasing
quantum dot the confinement is in 3D instead of just 1D, hence temperature, consistent with reducing thermal carrier concen-
the same confined energy level would be expected for a larger trations [21].
nanocrystal size. The data in Fig. 6a show that a level of 1.7 eV The activation energy (E act) for thermal activation of defects
is observed for a nanocrystal diameter of 2 nm — i.e. twice the is given by an Arrhenius relation, e.g. [22] p. 285:
width of that observed in the quantum well. This proportion is  m
supported by the effective mass theory. 1.7 eV is close to the qðT Þ=qc ¼ Tc =T expðEact =kT Þ
 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662 659

1.00E+04 0.030
Resistivity (Ω.cm)

0.025

0.020

1.00E+03 0.015 Activation energy, Eact (eV)

0.010

resistivity
0.005

Eact
1.00E+02 0.000
2.00 4.00 6.00 8.00 10.00 12.00 14.00
1000/T (1/K)

Fig. 7. Electrical resistivity and corresponding thermal activation energy of silicon QD superlattice layers in the lateral direction for a standard sample after
hydrogenation.

where k is Boltzmann’s constant, q is resistivity and subscript
g indicates q at a reference temperature, T g.
E act extracted from the slope of the plot in Fig. 7, is
approximately 17 meV between room temperature and 120 K
and approx. 10 meV down to 90 K before rising again around
80 K. This is indicative of a change of mechanism at lower
temperatures. However these are low activation energies and it
is too soon to determine the mechanisms involved [21]. Further
studies, using this technique, of material prepared in different
ways is providing information on conduction mechanisms and
their dependence on preparation conditions. The resultant data
on parameters such as thermal activation energies will enable
identification of the dominant transport mechanisms.
4.4. Alternative matrixes for Si quantum dots
Transport properties are expected to depend on the matrix in
which the silicon quantum dots are embedded. As shown in
Fig. 8, different matrixes produce different transport barriers
between the Si dot and the matrix, with tunnelling probability
Si3 N 4
SiC
1.9 eV
0.5 eV
c-Si 1.1 eV c-Si 1.1 eV c-Si
0.9 eV
2.3 eV
Fig. 8. Bulk band alignments between crystalline silicon and its carbide, nitride
and oxide.
heavily dependent on the height of this barrier. Si3N4 and SiC
give lower barriers than SiO2 allowing larger dot spacing for a
given tunnelling current.
The barrier to tunnelling between quantum dots is reduced
for a lower barrier height material, because that tunnelling
probability is given by, e.g. [23] p. 244:
( rffiffiffiffiffiffiffiffiffi )
8m4 1=2
Te ¼ 16 exp  DE I d
h/ 2
where m* is the bulk effective mass in the respective band of
the matrix, d is the spacing between dots and DE is the energy
difference between this bulk band and the band formed by
quantum dot interaction (DE = E c  E n). Hence the important
parameter in determining the degree of interaction between
quantum dots is m*DEId 2. As barrier height decreases the
barrier thickness for a given probability increases, thus
requiring lower dot density for a given conductivity or higher
conductivity for a given dot density. (In addition as dot size
decreases DE also decreases, thus increasing Te and enhancing
the effect further for smaller quantum dots.) [24]
Hence, transport between dots can be significantly increased
SiO2 as the barrier height decreases with alternative matrixes. The
spacing of dots would have to be closest in the oxide, nitride
and carbide, in that order. Similar deposition and quantum dot
3.2 eV
precipitation approaches should work for all.
4.5. Si quantum dots in a nitride matrix
1.1 eV
For the above reason we have explored application of
similar techniques to those described in Section 4 for SiO2, to
the growth of Si nanocrystals in silicon nitride by both
4.7 eV
sputtering and PECVD [25]. For sputtering, growth parameters
are very similar to the oxide but with growth from a Si and
Si3N4 target rather than from an oxide one. Results from
HRTEM are very promising (see Fig. 9), which shows
crystalline nanocrystals in the nitride matrix.
660 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662
Fig. 9. Sputtered Si nanocrystals in silicon nitride: HRTEM showing crystal
structure in nano-crystals.
In addition PECVD has been used for the growth of Si
nanocrystals in nitride with a similar regime of growing
alternate Si rich and stoichiometric nitride layers. Annealing
is carried out again at 1100 -C but with a pre-anneal at 500 -C
to drive off hydrogen incorporated from the PECVD process.
Again HRTEM images showing even clearer nanocrystals have
been obtained; see Fig. 10 [25].
Further optical and electrical characterisation is underway
on these nitride materials. Other authors [26] have published
data on Si QD in Si3N4 demonstrating crystallinity and
increased PL energy but not using the close control of QD
size that we have employed using the layering method.
5. Third generation application of Si nanostructures
As discussed in Section 3, silicon nanostructures are being
applied to Si based tandem cells and hot carrier cells.
5.1. Si based tandem cell
The data above show the significant progress made towards
formation of Si QD nanostructures and superlattices with
enhanced band gap (Figs. 4– 6 for oxide and Figs. 9 and 10 for
nitride), with good nanocrystal size control demonstrated. That
Fig. 10. PECVD Si nanocrystals in silicon nitride: HRTEM showing crystal
structure in nano-crystals.
these nanocrystals are quantum dots is demonstrated by the PL
data of Fig. 6. Methods to decrease the currently high
annealing temperatures for Si QD formation are also under
investigation, so as to increase compatibility with standard
solar cell fabrication. Those data in Fig. 7 show tentative
progress towards reasonable conduction, with a significant
increase on passivation of defects by hydrogenation. These
being the first challenges for a Si nanostructure tandem cell.
We have also made some progress on the other requirement
for a tandem cell element, that of junction formation in Si
nanostructures, with implementation of a Si QD SL/Si
anisotype heterojunction [17]. V OC was low and current very
low from this device and in itself it is not useful as a device
because any carriers generated in the high band gap region will
lose energy down to the Si band edge in the Si region. However
it is a useful proof of concept of junction formation.
The increased strength of optical processes in confined
structures due to localisation of electrons and holes, is highly
advantageous for solar cell structures, as it means that only
very thin layers of these dots are required for strong absorption.
With an appropriate light-trapping scheme, thin films of
unconfined Si of 1000 nm of Si give high solar absorption.
Quantum dot devices of only 100 nm thickness seem feasible
given the increased optical strength of the confined processes.
5.2. Hot carrier cell
As discussed in Section 3.2, Si nanostructures are applicable
to selective energy contacts but are as yet not being looked at
for hot carrier absorber materials.
Fig. 11. (a) Device structure with single layer of Si quantum dots sandwiched
by SiO2; (b) HRTEM of the structure showing the Si quantum dot layer.
 G. Conibeer et al. / Thin Solid Films 511 – 512 (2006) 654 – 662
Current density (A/m2)
0.8
0.7
0.6
0.5
0.4
Two different
sites on the wafer
0.3
0.2
0.1
0 Third generation photovoltaic devices aim to tackle the
0 0.25 0.5 0.75 1 1.25 1.5
Gate Voltage (V)
Fig. 12. I – V behaviour at 300 K of double barrier Si QD layer mesas, showing
NDR for two different devices on one wafer.
Double barrier resonant tunnelling contacts are being
investigated as selective energy contacts. Total energy filtering
is required of a selective energy contact rather than 1D energy
filtering. This is because the energy filtering in a quantum well
resonant tunnelling device (1D) is only effective for carriers
with momenta entirely perpendicular to the plane of the well
[11]. Carriers with components of momenta away from this
normal can be transmitted even if their total energy is outside
the range of the energy filter. Hence work in the Centre is
focussed on resonant tunnelling structures using quantum dots
or other discrete total energy confined centres as the resonant
centres. These would give the required total energy filtering.
Such a filter should exhibit negative differential resistance
(NDR) in all directions.
A significant proof of concept has been achieved with
negative differential resistance observed at room temperature
for a double barrier quantum dot structure [12]. The device
structure is based on our Si quantum dot technology discussed
above in Section 4 and is shown in Fig. 11.
The device uses a degenerately doped wafer and highly
doped capping layer to provide the conducting contacts either
side of the resonant structure. The layer of Si quantum dots and
oxide layers are grown by the reactive sputtering technique
discussed above in Section 4. 1 mm2 mesas were defined on
the sample surface before contacts were applied. The room
temperature I –V behaviour of two of these mesas is shown in
Fig. 12.
Fig. 12 shows definite evidence for NDR in this structure at
room temperature — a very encouraging result. The data are as
yet preliminary, only show limited repeatability and are not
particularly well peaked at the resonant energy. The voltage at
which resonance occurs is also rather high but the current
passed at this resonance is also high. Furthermore the NDR
observed is only in one direction and hence is only partial proof
661
of the total energy filtering required; however, it is a necessary
pre-requisite for total energy filtering. Nonetheless, together
with the evidence for quantum dot formation in the structure
shown in Fig. 11b, this represents a very encouraging proof of
concept of energy filtering.
Further work is now underway on similar structures,
refining the technique to investigate local I –V curves on the
scale of a few Si quantum dots, with the intention of improving
the quality factor of the resonant peak.
In addition, modelling of the 1D resonant tunnelling has
been carried out with a model developed for perturbations in
the position of a defect in an oxide barrier [10]. The theory is
being extended to a 2D model.
6. Conclusions
1.75
losses associated with the non-absorption of below band gap
photons and the thermalisation of above band gap photons to
the band edge. We are using nanostructures for the three main
approaches that have been suggested: tandem cells, hot-carrier
cells and up-conversion. For the first two of these, we are
investigating silicon based nanostructures for a Si based
tandem cell and selective energy contacts for a hot carrier cell.
We have also made progress towards up-conversion using Er
based phosphor nanostructures and the theory of hot carrier
cooling but as these are not Si based nanostructures they are
not discussed here in detail.
For the Si based tandem, the formation of Si QDs in oxide
and nitride matrixes has been demonstrated, with good dot size
control and observed nano-crystallinity, using cross-sectional
high resolution TEM. For the oxide, quantum confinement has
been demonstrated by photoluminescence, with PL energy
increasing as dot size decreases in agreement with effective
mass calculations. Initial resistivity measurements and early
attempts at junction formation are giving promising results.
For the hot carrier cells a significant proof of concept has
been achieved with double barrier Si QD resonant tunnelling
structures, which have exhibited negative differential resistance
at room temperature, a necessary pre-requisite for selective
energy contacts.
Acknowledgments
The Centre of Excellence for Advanced Silicon Photo-
voltaics and Photonics is supported by the Australian Research
Council.
We acknowledge work in the SIMS Facility of the
Australian Nuclear Science and Technology Org. Lucas
Heights, Sydney.
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