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Available online 13 August 2008 This paper will review the chalcogenide thin lm photovoltaic (PV) solar cells, based on cadmium
PACS: telluride (CdTe) and copper indium diselenide (CIS) and discuss the potential for metalorganic chemical
71.55.Gs vapour deposition (MOCVD) to enable more advanced devices in the second generation of CdTe module
73.40.Ei production. The current generation of production methods is based on physical vapour deposition (PVD)
73.61.Ga or close-spaced sublimation (CSS). This paper concentrates on the less well-known topic of MOCVD of
78.66.Jg thin lm chalcogenide cells, and in particular that of CdTe. Efcient CdTe PV solar cells (410% AM1.5)
have been demonstrated from deposition of the CdS, CdTe and CdCl2 lms in a single MOCVD chamber.
Keywords: The CdTe layer was doped with As and an additional high As concentration CdTe layer provides effective
A3. Metalorganic chemical vapour low resistance contacting without the need for wet etching the surface. The high level of exibility in
deposition
using MOCVD has been demonstrated where the CdS window layer has been alloyed with Zn to improve
B1. Cadmium compounds
the blue response of the PV device and improve AM1.5 efciency to 13.3%.
B2. Semiconducting IIVI materials
B3. Solar cells & 2008 Elsevier B.V. All rights reserved.
1. Introduction However, a new generation of thin lm plants are being built that
will have the order of 100 MW annual output. One of these
The urgent concern over climate change is rapidly transform- manufacturers, First Solar, is manufacturing CdTe PV modules
ing photovoltaic (PV) solar energy from a niche technology to one based on close-spaced sublimation (CSS) of the CdTe absorber.
which is entering the main stream of renewable energy genera- This paper will report on recent research results using metalor-
tion. The market growth has been sustained at 3040% per annum ganic chemical vapour deposition (MOCVD) as an alternative
since the 1990s and last year grew by a staggering 62% [13]. Over deposition method that could offer greater process exibility for
90% of this production is from crystalline silicon products, using advanced structures but new MOCVD technology would be
wafers of single-crystal or multi-crystalline silicon. The rest required to enable large volume production of PV modules.
comprises of various thin lm silicon materials, including
amorphous silicon, cadmium telluride (CdTe) and the copper
indium gallium diselenide (CIGS) family of materials. Over the 2. CdTe and CIS PV solar cells
past 4 years the latter two classes of materials (the chalcogenides)
have started to take their place in volume manufacture and In this section the application of MOCVD for laboratory scale
increased market share. PV solar module production prices are chalcogenide solar cells is reviewed. CdTe thin lm solar cells are
currently a factor of three too high to be cost competitive with typically deposited onto transparent conducting oxide (TCO)-
fossil fuel generation of electricity. Thin lm PV module coated glass substrates. This is known as the superstrate
manufacture is inherently lower cost than for crystalline silicon conguration approach. Alternatively, the CIS family of cells is
but the smaller production volume for thin lm PV has kept the deposited onto Mo-coated glass substrates, known as the sub-
price relatively high. Pearce [1] predicts that multi-megawatt per strate conguration approach. The main difference between these
annum production scale will decrease the cost to be price approaches are that for the superstrate the solar cell will receive
competitive, without the current subsidies operated in the major the solar radiation through the glass substrate whereas for the
PV adopter countries. Until recently, thin lm PV production substrate approach the solar radiation is received from the top of
factories had outputs in the region of only 10 MW per annum. the thin lm structure. These structures are represented schema-
tically in Fig. 1. In both cases the substrate material is polycrystal-
line or amorphous resulting in polycrystalline PV layers. A typical
Corresponding author. layer structure for CdTe is shown in Fig. 1 and comprises of the
E-mail address: stuart.irvine@optictechnium.com (S.J.C. Irvine). TCO for the front contact, a CdS n-type (window) layer and a CdTe
0022-0248/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2008.07.121
ARTICLE IN PRESS
S.J.C. Irvine et al. / Journal of Crystal Growth 310 (2008) 51985203 5199
5200 S.J.C. Irvine et al. / Journal of Crystal Growth 310 (2008) 51985203
Table 1
A comparison of process steps between conventional processing of CdS/CdTe solar 18
cells and those produced by MOCVD in a single chamber 16
14
Jsc (mA.cm-2)
Conventional processing MOCVD
12
Deposit CdS from chemical bath Deposit CdS 10
Anneal Deposit As-doped CdTe 8
Deposit CdTe by CSS Deposit high As cap CdTe layer 6
Deposit CdCl2 layer Deposit CdCl2 layer
4
Anneal Anneal
Chemical etch Deposit metal back contact 2
Deposit metal back contact 0
Anneal 1.E+15 1.E+16 1.E+17 1.E+18 1.E+19 1.E+20
As concentration (atoms cm-3)
S.J.C. Irvine et al. / Journal of Crystal Growth 310 (2008) 51985203 5201
prior to metallisation with Au. These conventionally processed 3.4. CdCl2 anneal
layers had series resistance of around 10 O cm2, which is too high
for an efcient device. Much higher series resistance was Arsenic doping of the CdTe layer was insufcient to achieve
measured for thick CdTe cap layers, probably due to the resistivity high-efciency CdTe/CdS PV devices, so the CdCl2 treatment step
of the layer itself. For thinner layers, approximately 200 nm, the was introduced. With the intention of carrying out all the
series resistance was reduced to below 2 O cm2. necessary steps in an MOCVD chamber, CdCl2 was deposited from
The mechanism for the reduced series resistance is not simply the precursors DMCd and tBuCl [23]. The MOCVD process differs
related to producing a p+layer although the carrier concentration from the conventional Cl treatment in being carried out in a single
does rise towards the surface. The need for high arsenic MOCVD chamber and does not involve any ex situ treatment.
concentrations 42 1019 cm3 could be related to the formation In contrast to the conventional, ex situ, Cl treatment, the As
of a second phase material near the surface. The remarkable result doping is still needed in order to obtain a high photo-current, to
of this process is the ease for which an evaporated gold contact, date, the results achieving 410% efciency, used a substrate
without any prior etching, can produce a low-resistance contact, temperature of 200 1C during deposition and 420 1C for 10 min for
removing the wet etching process step. the annealing. The choice of optimised parameters for the CdCl2
treatment will depend heavily on the thickness of the CdTe
absorber layer. It appears that most of the CdCl2 layer is consumed
20 while annealing, diffusing along the grain boundaries.
Series resistance/Ohm cm2
18
16 4. PV device results
14
12 A summary of device performance made using 5 5 mm2 Au
10 contacts onto MOCVD-grown PV structures is shown in Table 2.
8 The values from the table are taken over an average of three
6 devices (i.e. contact areas) as shown in Fig. 4, showing a
photograph of a test sample (25 17 mm2), ready for testing in
4
an AM1.5 solar simulator. Using the high-As concentration contact
2 layer, described in Section 3.3, there is no etching of the CdTe
0 surface prior to evaporation of the Au contacts.
0 200 400 600 800 1000 The results in Table 2 show average results for two different
Thickness of the heavily doped CdTe:As layer / nm device structures, one with the CdS window layer and the other
Fig. 3. Series resistance measured in PV cells with 5 5 mm2 Au contacts onto the
with the CdZnS window layer. Both achieved AM1.5 efciencies
highly doped As cap layer [23]. Estimated concentration of As in the cap layer is higher than the 10% target but it can be seen that the CdZnS
2 1019 cm3. window layer makes a substantial improvement in efciency
Table 2
Summary of device performance for 5 5 mm2 PV devices using all the MOCVD process steps and comparing CdS with Cd0.9Zn0.1S window layers
+
CdS (240 nm)/CdTe:As (2 mm)/CdTe:As (250 nm) 10.3 24 66 650
Cd0.9Zn0.1S (240 nm)/CdTe:As (2 mm)/CdTe:As+ (250 nm) 13.3 26 74 690
Fig. 4. Photograph of a test sample (25 17 mm2) ready for measurement of device PV performance. The three gold contact pads represent three separate devices that can
be used to test consistency and uniformity of the device structure.
ARTICLE IN PRESS
5202 S.J.C. Irvine et al. / Journal of Crystal Growth 310 (2008) 51985203
14
12
AM 1.5 efficiency
10
0
Undoped/ low As Optimum No As/ Optimum Optimum CdZnS
no cap (1E17 cm-3) As (2E18 CdCl2 cap As (2E18 As (2E18 window
/ no cap cm-3)/ no cm-3)/ cm-3)/ high layer
cap CdCl2 cap As contact/
CdCl2 cap
Device structure
Fig. 5. Comparison of AM1.5 PV efciency for different MOCVD process steps, as indicated.
above 13%. This is higher than any previous result for MOCVD- The concentrations of elemental As and Cl are far higher than the
grown CdTe absorber material. Looking at the device parameters it active acceptor concentration and it is not clear at this stage what
can be seen that the improvements have occurred not only from role the grain boundaries play in this process. Finally the ability to
the higher short circuit current (Jsc) with enhanced collection of change the composition of the CdS window layer to the CdZnS
blue photons, but also in open circuit voltage (Voc) and ll factor alloy has given a further boost in efciency to 13.3% and illustrates
(FF). The latter 2 parameters would indicate that the junction how MOCVD can now be used to engineer the CdTe PV device
quality has improved, indicating a lower defect density in this structure.
region. This effect is being investigated further and will be The future potential for MOCVD as a volume production
included in a more detailed paper on the alloy window layer. technique for thin lm solar cells depends on the ability to scale
A summary of all the MOCVD process steps is shown in Fig 5. this process to carry out each of the deposition steps as a
This shows the combination of optimum As doping, high As continuous in-line process. This could be used for deposition onto
contact layer, CdCl2 cap layer and the Cd0.9Zn0.1S window layer. glass substrates or onto exible substrates as a roll-to-roll process.
This demonstrates the importance of controlled As doping in Growth rates are currently too low to achieve the desired in-line
combination with the CdCl2 cap and anneal. The absence of process speed above 10 cm/min and new developments would be
signicant photocurrent with just the CdCl2 anneal might be needed in the deposition kinetics. The advantages in using
due to other changes that occur with ex situ annealed material in MOCVD would be in having an atmospheric pressure process,
the native defect concentration to make the CdTe layer p-type. with no wet chemical steps. The materials exibility in, for
These MOCVD process steps demonstrate the ability to engineer example, changing alloy composition could lead to higher-
the device using MOCVD that cannot be readily achieved by the efciency PV modules in production that are currently not
conventional annealing procedures to reach high-efciency achievable with CSS and CBD deposition techniques.
devices. This process avoids the need for chemical bath deposition
(CBD) and wet etch processes and is carried out at atmospheric
pressure, which is attractive for large scale production processes. Acknowledgements
S.J.C. Irvine et al. / Journal of Crystal Growth 310 (2008) 51985203 5203
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