CA2519608A1 - Quantum dot-polymer nanocomposite photodetectors and photovoltaics - Google Patents

Abstract

The present invention relates to photodetectors and photovoltaics and in particular lead sulphide quantum dot infrared photodectors and photovoltaic devices.
The present invention includes sensitizing conjugated polymers with infrared active nanocrystal quantum dots to provide a spectrally tunable means of accessing the infrared while maintaining the advantageous properties of polymers. The present invention uses such a nanocomposite approach in which quantum size effect-tuned PbS nanocrystals sensitize the conjugated polymer poly(2-methoxy-5-(2'-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) into the infrared. The present invention achieves, in a solution-processed device and with sensitivity far beyond 800 nm, harvesting of infrared-photogenerated carriers and the demonstration of an infrared photovoltaic effect. The present invention also exploits the wavelength tunability afforded by the nanocrystals to show photocurrent spectra tailored to three different regions of the infrared spectrum.

Description

QUANTUM DOT - POLYMER NANOCOMPOSITE PHOTODETECTORS AND
PHOTOVOLTAIC DEVICES
FIELD OF THE INVENTION
This invention relates to photodetectors and photovoltaics and in particular lead sulphide quantum dot infrared photodectors and photovoltaic devices.
BACKGROUND OF THE INVENTION
In contrast to traditional semiconductors, conjugated polymers provide ease of processing, low cost, physical flexibility, and large-area coverage.
These active optoelectronic materials produce and harvest light efficiently in the visible spectrum. The same functions are required in the infrared for telecommunications (1300-1600 nm), thermal imaging (1500 nm and beyond), biological imaging (800 nm and 1100 nm transparent tissue windows), thermal photovoltaics (> 1900 nm), and solar cells (800-2000 nm). Photoconductive polymer devices have yet to demonstrate sensitivity beyond 800 nm.
Organic/nanocrystal composites have been demonstrated to enable a number of important optoelectronic devices operating in the visible region. In the infrared, electroluminescence has been demonstrated from such materials. In the area of infrared photodetection using nanocomposites there is one report with a low internal quantum efficiency of 10-5 at 5 V bias that necessitated the use of modulated illumination and a lock-in amplifier to observe the photocurrent.
Thus far, there has been no demonstration of an infrared photovoltaic effect from such a material system.

Control of organic-inorganic interfaces on the nanoscale is of critical importance in organic electronics, and in particular in photovoltaic devices based on inorganic quantum dots embedded in a semiconducting polymer matrix. In these systems, rapid and efficient charge separation is needed for subsequent separate transport and extraction of electrons and holes. Organic ligands passivating the surfaces of nanocrystals are needed to enable solution-processing without aggregation, yet unfortunately these ligands are typically insulating and thus impede charge transfer between the nanocrystal and polymer. Moderate success has been achieved in conjugated polymer/ inorganic nanocrystal composite-based solar cells active in the visible region, and these hold the promise for fabrication of large area photovoltaics on flexible substrates using low-cost processing methods such as solution spin coating. However, approximately 50% of solar energy reaching the Earth's surface lies in the visible region, and the remainder in the infrared (1R) region beyond 700 nm. It is therefore of great interest to develop IR sensitive devices, ultimately to enable harvesting of the full solar spectrum.
Infrared photoconductive and photovoltaic devices based on the solution-processible PbS quantum dot / MEH-PPV materials system have recently been reported. These first reports exhibited promising efficiencies meriting further optimization. Many factors can affect photovoltaic device performance, such as the effectiveness of charge separation and the magnitude of charge mobility, as well as the efficiency of charge collection. It is fundamentally important to understand these processes and to increase the effectiveness of these

2 processes in the device in order to optimize performance.
SUMMARY OF THE INVENTION
The present invention is a nanocomposite layered device comprising: a transparent substrate; a hole conducting layer; a semiconducting polymer layer;
and a composite layer containing semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.
In another aspect the invention is a nanocomposite layered device comprising: a transparent substrate; a hole conducting layer; a semiconducting polymer layer; and a infrared-absorbing quantum dot nanoparticle layer.
In a further aspect the invention is a nanocomposite comprising a semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.
In a still further aspect the invention is process for producing a nanocystal composite layer comprising the steps of:
synthesizing quantum dot nanocrystals to produse nanocrystals capped with synthesized ligands;
exchanging the synthesized organic ligands with a new organic ligand to produce ligand-exchanged nanocrystals;
redispersing the ligand-exchanged nanocrystals in a solvent which is compatible with the solution-processing of the combined polymer-quantum dot dispersion to produce a prepared nanocrystal;
mixing prepared nanocrystals with the polymer matrix material in a

3 predetermined percentage by weight to produce a nanocrystal composite layer.
In a further aspect of the invention is a process for producing a nanocomposite layered device comprising the steps of:
providing a transparent substrate;
coating the transparent substrate with a hole conducting layer to produce a coated substrate;
coating the coated substrate with a semiconducting polymer layer to produce a polymer coated substrate;
coating the polymer coated substrate with a infrared-absorbing quantum dot nanoparticle layer to produce a nanocomposite layered device.
Sensitizing conjugated polymers with infrared active nanocrystal quantum dots provides a spectrally tunable means of accessing the infrared while maintaining the advantageous properties of polymers. The present invention uses such a nanocomposite approach in which quantum size effect-tuned PbS
nanocrystals sensitize the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) into the infrared. The present invention achieves, in a solution-processed device and with sensitivity far beyond 800 nm, harvesting of infrared-photogenerated carriers and the demonstration of an infrared photovoltaic effect. The present invention also exploits the wavelength tunability afforded by the nanocrystals to show photocurrent spectra tailored to three different regions of the infrared spectrum.
The present invention generally demonstrate, using solution-processed materials, both a three-order-of-magnitude improvement in infrared

4 photoconductive internal quantum efficiency compared to, allowing observation of the photocurrent under continuous-wave illumination without reliance on lock-in techniques; and also the first observation of an infrared photovoltaic effect in such materials. Under -5 V bias and illumination from a 975 nm laser, detectors of the present invention show an internal quantum efficiency of 3%, a ratio of photocurrent to dark current of 630, and a maximum responsivity of 3.1 x 10-3 A/W. The photovoltaic response under 975 nm excitation results in a maximum open circuit voltage of 0.36 V, short circuit current of 350 nA, and short circuit internal quantum efficiency of 0.006%. The present invention also demonstrates, by varying the size of the nanocrystals during processing, photocurrent spectra with peaks tailored to 980 nm, 1.200 pm, and 1.355 pm.
Further features of the invention will be described or will become apparent in the course of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described by way of example only, with reference to the accompanying drawings, in which:
Figures 1 a and 1 b show dark current and photocurrent versus applied bias at the ITO electrode wit hthe pump powers shown in the figure legends, Figure 1 a, the main panel shows the dark current and photocurrent results for a sample with ~90% by weight nanocrystals in the polymer/nanocrystal blend, Figure 1 a inset shows dark current for the main panel, Figure 1 b, the main panel shows the dark current and photocurrent curves near zero bias, demonstrating the

5 photovoltaic effect;
Figures 2a and 2b show photocurrent and internal quantum efficiency versus incident optical power, Figure 2a shows the photocurrent in red (circles) on the left axis and the internal quantum efficiency (squares) in black on the right axis are shown as a function of incident power at -5 V bias, Figure 2b, main panel shows short circuit current (circles) and corresponding internal quantum efficiency (squares) as a function of incident power;
Figure 3 shows photocurrent spectral responses and absorption spectra in which the main panel shows photocurrent spectral response (symbols) and the corresponding absorption spectra (solid line) for three different samples and the inset shows extended spectral response for the sample centered at 955 nm;
Figure 4 shows the absorption spectrum of PbS-nanocrystal / MEH-PPV
composite film measured in reflection mode;
Figure 5(a) shows the absorbance spectra for two samples before and after annealing. The bottom two curves are the absorbance for the sample (S1 ) annealed at 160 °C and the top two curves are for the sample (S2) annealed at 220 °C. The inset is the absorbance near the PbS nanocrystal first exciton peak for S2. For clearer comparison, the top two curves have been up-shifted;
Figure 5(b) shows photocurrent spectral responses near the PbS
nanocrystal absorption peak for an unannealed sample (bottom curve), and the samples annealed at 190 °C (middle curve) and 220 °C (top curve). The photocurrent of the annealed sample is about two orders of magnitude larger

6 than the unannealed sample for the same incident light intensity. In the figure, the data are rescaled or shifted up to identify the peaks, the inset shows the normalized photoluminescence before annealing; the photoluminscence was undetectable after annealing, the data in both the main figure and the inset have been smoothed;
Figure 6(a) shows the dependence of the short circuit current, open circuit voltage, and fill factor (FF = maximum output/(IS~ * V°~)) on the incident optical power for the device annealed at 220 °C, the inset plots I-V curves with and without illumination for the sample annealed at 220 °C;
Figure 6(b) shows plots of the dark current (~, at bias of -1 V), photocurrent Ip,, (~,at bias of -1 V and illumination light power of 16 mW), and short circuit current ISO (~, at illumination power of 400 mW) vs. the annealing temperature, the solid line is an exponential fitting curve, the inset plots the normalized ISO and product of ISO*V°~ (under 400 mW illumination), where ISO and ISO*Vo~ of the unannealed sample are assumed as 1;
Figure 7 shows temporal behaviour of ISO for the unannealed sample (bottom curve) and sample annealed at 220°C;
Figure 8 shows normalized weight vs. the temperature from TGA for an unexchanged sample (i.e. with the oleate ligand) and a fully octylamine exchanged sample; and Figure 9 shows TEM cross-section images for an unannealed sample (A
and B), and for the samples annealed at 190 (C and D) and 220 °C (E and F), respectively. The three figures on the left hand side are low magnification

7 images (x 150K), and the figures on the right hand sides are high magnification images (x 500K).
DETAILED DESCRIPTION OF THE INVENTION
PbS quantum dot nanocrystals were chosen for their ability to sensitize MEH-PPV, which on its own absorbs between 400 nm and 600 nm, into the infrared. The nanocrystals of the present invention have absorption peaks tunable from 800 nm to 2000 nm'3. The present invention shows herein that a devices' photocurrent spectrum corresponds to the nanocrystals' absorption spectrum, indicating that the sensitivity of the nanocomposite could potentially be tuned across the 800 - 2000 nm spectral region.
The selection of the semiconducting polymer is important to achieving charge separation between the nanocrystal and polymer. Conjugated polymers typically have better hole than electron mobility. Thus, photoconductivity in polymer/nanocrystal composites requires a band alignment that favors transfer of the photogenerated hole to the polymer; that is, the ionization potential of the polymer should, ideally, lie closer to vacuum than that of the nanocrystal.
The bulk ionization potential of PbS is 4.95 eV, while most conjugated polymers have ionization potentials greater than ~5.3 eV'4. The low ionization potential of PbS relative to other semiconductor materials used in nanocrystal-based photoconductive devices such as the cadmium chalcogenides (bulk ionization potentials between ~6.4 eV and ~7.3 eV) limits the number of readily available conjugated polymers that provide a favorable energy alignment. MEH-PPV was

8 selected for its low ionization potential, variously reported between ~4.9 eV
and ~5.1 eV'S,~s. It was not obvious at the outset that MEH-PPV/PbS would provide the type-II heterojunction needed for efficient photoconduction and for the observation of a photovoltaic effect: the vacuum-referenced band edge of the organic component is uncertain; it is possible that a dipole layer could be formed at the interface between materials, altering the effective band alignment; and the nanocrystal energy levels vary with size. However, MEH-PPV was one available conjugated polymer candidate to provide the correct heterostructure for this application.
The devices consist of a sandwich structure of glass, indium tin oxide (1T0), polyp-phenylenevinylene) (PPV), MEH-PPV/PbS nanocrystal blend, and an upper Mg contact. In addition to acting as a hole transport layer, the PPV
layer provides a number of improvements over samples with the MEH-PPV/nanocrystal layer deposited directly on the ITO: it provides better electrical stability by forming a smooth and pinhole-free pre-layer on which the blend films can be cast, eliminating catastrophic shorts from the upper contact directly through to the ITO; it decreases the dark current by introducing an injection barrier at the ITO contact, allowing larger photocurrent to dark current ratios; and it allows a higher bias to be applied to the samples before electrical breakdown, allowing the establishment of a higher internal field, more efficient photogenerated carrier extraction, and consequently higher photocurrents.
The PPV layer slightly reduces the photocurrent internal quantum efficiency because it also poses a barrier to the extraction of both

9 photogenerated holes in the reverse bias and photogenerated electrons in the forward bias; (it will be shown below that the barrier to extracting holes from the active region is less than that for electrons, resulting in higher photocurrent in the reverse bias). However, the PPV layer poses less of an extraction barrier than it does an injection barrier, which allows for the improved photocurrent-to-dark-current ratio. The slight reduction in efficiency was a compromise to obtain low dark current and to maximize the on:off ratio, of critical importance in detection and imaging applications.
Figures 1 a and 1 b shows dark current and photocurrent versus applied bias at the ITO electrode. The data were taken using an Agilent 4155C
Semiconductor Parameter Analyzer and microprobe station. The optical excitation was provided by a 975 nm continuous-wave semiconductor laser, which allowed selective excitation of the nanocrystal phase. The pump powers are shown in the figure legends. In Figure 1 a, the main panel shows dark current and photocurrent results for a sample with ~90% by weight nanocrystals in the polymer/nanocrystal blend. The inset in Figure 1 a shows dark current for the main panel and shows the dark current is 216 nA at a bias of 5 V and 144 nA at -5 V. The photo I-V curves show diode-like behaviour, with higher photocurrents in the reverse bias. At a bias of -5 V, the photocurrent is 8.43 pA for 2.7 mW
incident power and 90.61 E.iA for 207 mW incident power, which represents a ratio of photocurrent to dark current of 59 and 630, respectively. The above photocurrent under 2.7 mW illumination represents a responsivity of 3.1 x10-3 A/V1I. When ITO is positively biased at 5 V, the photocurrent is reduced to 5.39 and 28.12 ~A for incident powers of 2.7 and 207 mW, respectively.
In Figure 1 b, the main panel shows dark current and photocurrent curves near zero bias, demonstrating the photovoltaic effect; these data were obtained from a different sample than shown in Figure 1 a and represent the best results to date for short circuit current and open circuit voltage. The inset shows a proposed simplified band diagram after the Mg electrode has been deposited and the sample reaches equilibrium.
The asymmetry of the photocurrent I-V curves can be ascribed to the work function difference between ITO (~4.8 eV) and Mg (3.7 eV) and to the energy levels of the PPV layer. The inset of Figure 1 b shows a possible band diagram for the structure after the Mg contact has been deposited, and the device reaches the equilibrium state. For this diagram, the lowest energy absorption peak is assumed to be the first excitonic absorption of the PbS nanocrystals.
This is used to estimate an increase in bandgap energy relative to bulk PbS, which has a bandgap of 0.41 eV; for the nanocrystals with absorption peaks centered at 955, 1200, and 1355 nm depicted in Figure 3, the effective bandgaps are 1.30, 1.03, and 0.92 eV, respectively. Because of the nearly equal effective masses for holes and electrons in PbS, it is also assumed that the confinement energy is shared equally in the conduction and valence bands so the bands move up and down, respectively, by equal energies. The barrier for electrons comes from the octylamine ligand, which passivates the nanocrystal surface, and/or the MEH-PPV (ionization energy ~4.9 eV and electron affinity ~2.9 eV'S), which surrounds the nanocrystal. To align the Fermi level in all layers, the Mg side tilts down and the ITO side tilts up. (Similar band tilting in polymers and in Cso doped polymers sandwiched between two different conductors have been discussed by Greczynski et al" and Brabec et a1'$, respectively). After an electron in the valence band of the nanocrystal is transferred to the conduction band by absorbing a photon, the hole in the valence band may transfer to the hole conducting MEH-PPV, and the electron can either remain in the quantum dot or move through the nanocrystal network by hopping or tunnelling.
Depending on the polarity of the built-in and/or applied field, the electron and hole can move towards the ITO or towards the Mg.
When the electron moves to the ITO side, it will see a higher barrier by the tilted band and PPV (ionization energy ~ 5.1 eV and electronic affinity ~ 2.7 eV's) than when moving to the Mg electrode. When the hole moves to the ITO, it also faces a barrier between MEH-PPV and PPV, and no barrier if it moves to the Mg side. Reverse bias results in photogenerated holes being extracted through the ITO/PPV side of the sample, while forward bias results in electrons being extracted through that side. Thus, the higher photocurrent in the reverse bias suggests that the electron barrier posed by the PPV may be more severe than the hole barrier in carrier extraction.
Figure 1 b shows dark and illuminated I-V curves for the region near 0 V, demonstrating the presence of a photovoltaic effect under continuous-wave illumination at 975 nm. The maximum short circuit current is 350 nA for an incident power of 207 mW. The open circuit voltage is 0.36 V. The photovoltaic effect was checked for hysteresis effects to see whether slow charge reorganization alone could be the cause. A sample demonstrating much lower short circuit current (~15 nA) than shown in Figure 1 b was used to provide more convincing evidence that, even with very low short circuit currents, the effect is not simply a hysteretic artefact.
The inset of Figure 2b shows the result of this test where the sample was held at zero bias and the short circuit current monitored over 500 seconds:
the signal was stable over this time span. Further evidence that the effect was not hysteresis-based was provided by performing voltage scans in both directions (forward bias to reverse bias and vice versa); the direction of scan had negligible effect on the photovoltaic response. Although this photovoltaic response, which allows separation of an electron-hole pair at zero applied bias, could be indicative of a type-II heterostructure between the PbS nanocrystals and MEH-PPV, the built-in field in the device under zero bias is significant and could also allow charge separation with a marginal type-I heterostructure.
Figures 2a and 2b show photocurrent and internal quantum efficiency versus incident optical power. Figure 2a shows the photocurrent in red (circles) on the left axis and the internal quantum efficiency (squares) in black on the right axis are shown as a function of incident power at -5 V bias. The internal quantum efficiency is defined as the ratio of the number of collected charges to the number of absorbed photons at the pump wavelength. The calculation of internal quantum efficiency using absorption values obtained in reflection mode, the handling of optical interference effects, and the range bars on these efficiency values are described in detail in the Methods section.

In Figure 2b the main panel shows short circuit current (circles) and corresponding internal quantum efficiency (squares) as a function of incident power. The lines are merely provided to guide the eye. Inset: Stability of the short circuit current as a function of time for a sample with much lower photovoltaic response than in Figure 1 b.
The percent absorption at the 975 nm wavelength used to obtain the main efficiency points in Figures 2a and 2b was 12.7%; the upper and lower range bars represent upper and lower bounds obtained based on the consideration of multiple pass propagation through the active layer. From the figure it can be seen that the photocurrent does not increase linearly with incident power.
Above ~50 mW, the photocurrent increases more slowly with increased power. In the low power region, the recombination of trapped electrons in the nanocrystal network with holes in the neighboring polymer dominates. When more photons are absorbed at higher powers, bimolecular recombination between free holes and electrons occurs in addition to the recombination at electron trap centerss.
The additional bimolecular recombination reduces the number of photo-excited carriers and, hence, lowers the internal quantum efficiency as shown in Figure 2a. At an incident power of 2.7 mW the internal quantum efficiency is about 3%
(ie. external quantum efficiency of 0.38%), while at 207 mW the internal quantum efficiency is reduced to about 0.4%.
The short circuit current and corresponding internal quantum efficiency is plotted in Figure 2b, showing a maximum value of 0.006% (ie. short circuit external quantum efficiency of 0.0008%). These zero bias internal quantum efficiencies are about 500 times lower than at -5 V and show similar signs of a roll-off caused by bimolecular recombination at higher powers. The short circuit internal quantum efficiency is much lower than the best reports in the literature for CdSe nanocrystal-based systems where the trioctylphosphine oxide (TOPO) ligands were removed by treatment with pyridine; for samples with the TOPO
ligands still present on the nanocrystal surface, these systems showed internal quantum efficiencies closer to, but still slightly higher than, the magnitude reported here8~2°. Further efforts are required in the PbS system to remove the ligands, potentially markedly improving efficiencies (especially in photovoltaic mode) in system of the present invention.
The 3% internal quantum efficiency at -5 V is a three order-of-magnitude increase over that reported in Ref. 12 and is attributed principally to an improvement in film quality across these large-area devices. The MEH-PPV in previous work was typically cast from toluene and was not ultra-sonicated or filtered. In the present report, the MEH-PPV was cast from chloroform, ultra-sonicated for 1 hour prior to casting the films, and both the polymer and nanocrystal solutions were independently filtered. The combination of the above treatments was shown using atomic force microscopy to provide smoother, more defect-free and pinhole-free films compared to the previous process.
The films produced as in Ref. 12, showed large centers of aggregated material and many pinholes; the newer films show much smaller regions of aggregated, transport-impeding material, and are pinhole-free. The improved surface of the films reported herein allows better interfacial contact with the upper metal electrode resulting in better carrier extraction2'. Films in the earlier work only contained ~60% nanocrystal by weight because this was the maximum loading that gave films which did not suffer from excessive shorts. In this work, films containing 90% nanocrystal by weight were successfully cast by optimizing the concentration, and hence viscosity, of both the nanocrystal and polymer solutions. The increased nanocrystal loading likely resulted in improved electron transport. Pinholes previously led in Ref. 12 to a photocurrent-to-dark-current ratio of ~10-4, necessitating the use of lock-in techniques to detect the photocurrent signal. The devices presented herein, with their orders-of magnitude greater photocurrent-to-dark ratios and efficiencies, were readily studied using continuous-wave methods.
Figure 3 shows the absorbance spectrum of the nanocrystals (measured using a Varian CARY 500 Scan Spectrophotometer) used in three different devices, each tuned to a different part of the infrared spectrum, and the measured photocurrent spectral response of each device. The main panel shows the photocurrent spectral response (symbols) and the corresponding absorption spectra (solid line) for three different samples. The absorption peaks are tuned to 955 (black), 1200 (red), and 1355 nm (blue). No bias was applied to the devices during measurement of the photocurrent spectrum, and the excitation was provided by narrow wavelength bands selected from a white light source by a monochromator. At wavelengths longer than 600 nm, the absorption of MEH-PPV is negligible; thus, all absorption at these wavelengths is assigned solely to the PbS nanocrystals. The absorption peaks at 955, 1200, and 1355 nm correspond to the first excitonic absorption features in the three different choices of PbS nanocrystals. The photocurrent spectra show peaks that match closely the absorption peaks associated with the nanocrystals. Along with demonstrating control over the spectral response, this result adds further evidence that the photocurrent is due to exciton formation in the nanocrystals followed by charge separation.
The inset in Figure 3 shows extended spectral response for the sample centered at 955 nm, shows the spectral response of the device with the 955 nm response peak, including shorter wavelengths where the polymer is also excited indicating the response in the region below 600 nm where both the polymer and nanocrystal are excited. Also shown are the absorption spectra of the polymer and the nanocrystals. The photocurrent response peaks at a wavelength 60 nm red-shifted relative to the polymer absorption peak.
In summary, large-area-compatible quantum dot infrared photodetectors have been fabricated via solution processing. The active layer is a composite of the conjugated polymer MEH-PPV and PbS nanocrystals. The devices show a maximum photocurrent to dark current ratio of 630 at a bias of -5 V. An internal quantum efficiency at -5 V as high as 3% has been achieved. The devices demonstrate a photovoltaic response under 975 nm continuous-wave excitation where the maximum short circuit current was 350 nA and the open circuit voltage was 0.36 V. The maximum short circuit (photovoltaic) internal quantum efficiency was 0.006%. The spectral response of the photocurrent closely followed the absorption of the nanocrystals and was shown for three different regions of the infrared spectrum. The internal efficiencies, improved from previous work, will benefit from further improvements once refined control over the ligand barrier is obtained.
Methods PbS nanocrystal synthesis and ligand exchange:
The synthesis followed that used in Ref. 13. The as-prepared nanocrystals were capped with oleic acid ligands. A post-synthesis ligand exchange was performed to replace these with octylamine ligands. The original oleic acid-capped nanocrystals were precipitated with methanol, dried, and dispersed in an excess of octylamine. This solution was heated at 70°C
for ~16 hours. After heating, the octylamine capped nanocrystals were precipitated with N,N-dimethylformamide and redispersed in chloroform. The nanocrystals were then mixed with MEH-PPV to give a known weight fraction.
1 ) Device processing A 40 nm poly(p-phenylenevinylene) (PPV) hole transport layer was spin-coated on 2.5 x 2.5 cm2 indium tin oxide (1T0) coated glass slide and annealed at 200°C for 3 hours in vacuum to allow polymerization. A MEH-PPV/nanocrystal blend (90% nanocrystal by weight of PbS nanocrystals to MEH-PPV) dissolved in chloroform was spin-coated on the PPV layer to form a film of thickness 100 -150 nm. Finally, the upper contact was deposited by vacuum evaporation forming a 3 mm2 metal stack of 150 nm Mg/100 nm Ag/10 nm Au.
2) The measurement of photocurrent spectral response.

0 V bias was applied to the sample connected in series with a load resistor of 100 S2, which was about three orders of magnitude smaller than the resistance of the sample. Illumination was provided by a white light source dispersed by a monochromator (Triax 320) and mechanically chopped at a frequency of 250 Hz. Various filters were used to avoid overtones of the monochromator's grating from illuminating the sample. The potential drop across the load resistor was read by a lock-in amplifier (Model SR803 DSP). The light intensity at each wavelength was separately measured. Then, the photocurrent at each wavelength was scaled to the same incident light intensity by assuming that the photocurrent was linearly proportional to the light intensity in the low intensity region used.
3) Calculation of internal quantum efficiency:
The percent absorption used in the internal quantum efficiency calculation needs to account for the device structure, which creates multiple optical passes due to the mirror-like upper metallic contact. Hence, optical interference effects must be considered22. Two separate approaches were taken and the results compared. First, the device's absorption was directly measured in reflection mode (Supplementary Figure).
For the second method, the single-pass absorption was measured and scaled by a factor determined by the intensity enhancement created by interference. Using a multilayer program, it was determined that the maximum enhancement would be between 2 and 2.5 depending on the exact layer thickness and index of refraction of each layer. Because there is a considerable amount of uncertainty in these values the more severe absorption enhancement factor of 2.5 we chosen to provide a conservative lower bound on efficiency.
The single-pass absorption was used as the lower bound on absorption (ie. upper bound on efficiency) to represent that case where negligible Fabry-Perot enhancement occurs. The intermediate efficiency points in Figure 2 where obtained using the measured multi-pass absorption at 975 nm (12.7%), and the upper and lower bounds where obtained using the single-pass absorption at 975 nm (7.9%) and 2.5 enhancement absorption at 975 nm (19.8%), respectively.
Sensitizing conjugated polymers with infrared active nanocrystal quantum dots provides a spectrally tunable means of accessing the infrared while maintaining the advantageous properties of polymers. Such a nanocomposite approach was used in which quantum size effect-tuned PbS nanocrystals sensitize the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) into the infrared. The present invention achieves, in a solution-processed device and with sensitivity far beyond 800 nm, harvesting of infrared-photogenerated carriers and the demonstration of an infrared photovoltaic effect. The present invention also exploits the wavelength tunability afforded by the nanocrystals to show photocurrent spectra tailored to three different regions of the infrared spectrum.
The present invention demonstrates, using solution-processed materials, both a three-order-of-magnitude improvement in infrared photoconductive internal quantum efficiency compared to, allowing observation of the photocurrent under continuous-wave illumination without reliance on lock-in techniques; and also the first observation of an infrared photovoltaic effect in such materials. Under -5 V bias and illumination from a 975 nm laser, detectors of the present invention show an internal quantum efficiency of 3%, a ratio of photocurrent to dark current of 630, and a maximum responsivity of 3.1 x 10-3 A/W. The photovoltaic response under 975 nm excitation results in a maximum open circuit voltage of 0.36 V, short circuit current of 350 nA, and short circuit internal quantum efficiency of 0.006%. The present invention also demonstrates, by varying the size of the nanocrystals during processing, photocurrent spectra with peaks tailored to 980 nm, 1.200 p.m, and 1.355 p.m.
The present invention took the approach that thermal treatment of the nanocomposite films could result in dramatically enhanced hole transfer from PbS quantum dots to the polymer matrix by increasing the intimacy of contact between the inorganic and polymer phases, potentially via the displacement of some ligands contacting the nanocrystal surfaces, allowing portions of the polymer chains to interact with the nanocrystal surface without the ligand barrier present. A number of reports in the literature have investigated the effects of annealing on polymer-based photovoltaic systems, typically citing changes in film morphology as the cause for improved charge separation or charge mobility.
There are a couple of reports related to the effect of annealing on optoelectronic devices consisting of organic/inorganic nanocrystals. An increase in dark current and photocurrent was observed in TOPO-capped CdSe nanocrystal solids upon thermal annealing. In solar cells consisting of pyridine capped CdSe in P3HT, Huynh et al. reported an increase in external quantum efficiency by a factor of 1.3 to 6, depending on the nanocrystal size, by heating the films. The removal of the ligand, and the reduction in NC separation have been used to explain the observed electrical and optical changes. The effect of annealing on bilayer or blend photovoltaics is remarkable. However, all of the above studies are related to solar cells working in the visible spectral region. No reports are related to the influence of annealing on photovoltaics made from blends of organic and small band gap inorganic materials, which can be used in the infrared region. The present invention shows herein, that thermal annealing of MEH-PPV / PbS nanocrystal films results in increased dark conductivity and a more rapid photoconductive response, as well as up to a 200-fold improvement in short-circuit current and 600-fold increase in maximum power output. The maximum monochromatic power conversion efficiency achieved upon annealing was 0.001 % under 16 mW illumination at 975 nm. The short circuit internal quantum efficiency of annealed samples is about 0.15%, compared to 0.0064%
for the best sample reported in Ref. 23. It is of scientific interest to study the role of the ligand and nanocrystal/polymer phase interaction on photovoltaic device performance. It is also of practical importance to achieve higher performance photovoltaic devices by replacing, in the solid state, the high and wide potential barriers for carriers posed by the organic ligand - especially when a ligand with a lower barrier, suitable for solution processing with the polymer, is not available.
The effects of thermal annealing on the absorbance features of MEH-PPV
/ PbS nanocrystal thin films spin-coated on indium tin oxide (1T0) are shown in Figure. 5. As shown by the bottom two curves (S1 in Figure 5), annealing at or below 160°C does not significantly change the absorption spectrum.
However, annealing at or above 190°C results in a blue-shift of the MEH-PPV peak centred at 500 nm, with the magnitude of the peak shift dependent on the annealing temperature. Annealing at 220°C leads to a peak shift to 480 nm from 503 nm, as shown by the top two curves (S2 in Fig. 5). Annealing at 190°C resulted in a peak shift of only about 9 nm. Films of MEH-PPV only, i.e. without PbS nanocrystals present, also demonstrated the same blue-shift in the absorption spectra, indicating that the MEH-PPV was responsible for the absorption change.
As illustrated by the inset in Figure 5, annealing at 220°C also slightly modifies the absorption shoulder near 1340 nm of the PbS nanocrystals. This change is negligible when the samples are annealed at less than 190°C.The blue shift of the MEH-PPV absorption peak after annealing is unexpected, and the reason is not entirely clear at this time. Annealing of conjugated polymers usually results in closer contact between the polymer chains, and this aggregation of the polymer generally leads to a red shift in the absorption band and photoluminescence peak. However, Nguyen et al. concluded from AFM
measurements that annealing above the polymer's glass transition temperature can slowly untangle seriously aggregated chains by allowing them to flow freely.
Shown in Figure 5 (b) are the photocurrent spectral responses of separate devices near the PbS nanocrystal absorption peak for an unannealed sample (bottom curve), and samples annealed at 190 °C (middle curve) and 220 °C (top curve). A well-defined photoconductivity peak is observed near 1330 nm before annealing, but this peak is red-shifted slightly after thermal annealing. For the sample annealed at 220 °C, the photoconductivity peak shifts ~20 nm.
Annealing affects the photoluminescence spectrum of the nanocrystals much more dramatically than the absorption and photocurrent spectra. Before annealing, all samples are photoluminescent with a peak near 1500 nm (see Fig. 5 (b) inset);
the 170 nm red-shift of photoluminescence from the absorption peak is attributed to the global Stokes shift. After annealing, the photoluminescence from the nanocrystals could no longer be detected, strongly suggesting improved charge transfer between the nanocrystals and polymer leading to photoluminescence quenching.
Figure 6 (a) shows the dependence of the short circuit current, open circuit voltage, and the fill factor [(V~I)~,aX/(Isc * V°o)l on the incident light power for a device made from a film annealed at 220°C. Plotted in the inset of Fig.
6 (a) are I-V curves for such a device in the dark and under illumination. The magnitude of short circuit current (ISO) and open circuit voltage (V°°) observed under illumination depends on the incident light intensity and annealing temperature.
Under 400 mW of illumination, a short circuit current of 25.5 NA has been observed from this device, compared with 17 pA in the 190°C annealed sample, and 0.13 pA in the unannealed sample. Below 150 mW, ISO increases linearly with power, as illustrated by the bottom curve in Figure 6(a). Under higher illumination intensity, ISO depends sublinearly on the light power, which may be ascribed to a bi-molecular recombination process.
The power conversion efficiency (maximum electrical output power/incident light power) is about 0.001 % at an incident power of 16mW and decreases with increased power. The low absorbance (<0.06) at the wavelength of illumination is a major reason for the low power conversion efficiency.
From the inset in Fig. 6 (a), it can be seen that the photocurrent under bias between 0 and Vo~, strongly depends on the electrical field. The absolute current is reduced almost linearly from ISO at 0 bias with the built-in field strength (Vo~active region thickness) to zero current at Vo~ (total field strength = 0), which indicates that the product of the charge mobility and the lifetime is small even in the annealed devices. Hence, charge extraction strongly relies on the electric field and charge diffusion contributes little to the photocurrent. This explains why the fill factor in the device herein is only 26%, and is almost independent of incident intensity. V°~
increases sublinearly with light power at low illumination, then saturates at higher power.
Similar to the ISO, the enhanced bimolecular recombination may be responsible for the dependence of V°~ on the illumination power. In all of samples herein, V°~ never exceeds 0.36 V, which is much smaller than the work function difference between ITO (4.55 eV) and Mg (3.8 eV). Similar results are reported in polymer/fullerene solar cells. It has been observed that the V°~
depends more on the reduction potential of the fullerene, which is aligned with the cathode's Fermi level, than on the metal's work function. The Vo~ is also reported to be strongly related to the oxidation potential of the polymer, which is aligned with the anodic Fermi level. However, in all these reports V°~ is not equal to the difference between the oxidation potential of the polymer and the reduction potential of the fullerene. Film morphology, Columbic energy, and polarization of the medium can all affect the magnitude of V°°. The results herein cannot give an explicit explanation for the limitation of V°°.
The dependence of dark current (at -1 V bias), photocurrent (at -1 V bias and optical excitation power of 16 mW), and IS° (at an illumination power of 400 mW) on the annealing temperature is shown in Figure 6(b). Each increases exponentially with annealing temperature, though the dark current increases at a different rate (note the scale difference in the vertical axes). Compared with the unannealed sample, the sample annealed at 220°C shows a dark current times higher, an IS° 200 times higher, and a product of IS° and V°° under 400 mW
illumination about 600 times higher. The inset in Figure 6(b) plots the ratios between annealed and unannealed samples for IS° and the product of (1S° * V°°).
Figure 7 shows temporal photocurrent behaviour of IS° for the unannealed sample (bottom curve) and sample annealed at 220°C (upper curve).
Switching the laser off/on or on/off causes an IS° decay to some value following a quick rise, or an IS° rise following a quick drop, respectively, for both samples.
The annealed sample, however, has a smaller decay, reaching the stable state much more quickly than the unannealed sample. Both the decay and rise processes can be fit with an exponential curve; the difference in time constant between the two samples is one order of magnitude. For the rise process:
ISO ~ -0.033 exp(-t/0.0178) for the as-deposited sample IS° ~ -0.032 exp(-t/0.00168) for the annealed sample where IS° at the equilibrium state under no illumination is assumed to be zero.
The temporal behaviour at zero bias results from charge trapping and releasing processes. During the illumination state, more electrons are trapped at the cathode and more holes at the anode, which gradually screens out the built-in field and diminishes the current. In the dark state, the trapped charges are released and may move in the negative direction to return to the equilibrium state (as shown by the negative current pulse).
Thermal gravimetric analysis (TGA) and transmission electron microscopy (TEM) were used to analyze the change in film structure and constitution caused by annealing. The TGA trace shown in Figure 8 for an unexchanged sample (i.e.
with the oleate ligand) and a fully exchanged octylamine-capped sample of PbS
nanocrystals indicates three temperature regions where weight loss occurs at a different rate(A, B and C in Fig. 8) In region A between 70°C and 200°C, the unexchanged sample lost very little weight, however, the fully exchanged sample lost about 5% of its weight. Considering the 175°C boiling point of octylamine and the difference in TGA data between unexchanged and exchanged samples, it is likely that in this temperature region the octylamine is being evaporated. In region B between 200 and 300°C, both samples lost weight with a relatively low rate.. In region C between 300 and 500°C, the unexchanged sample lost most of its weight (about 25%) and the fully exchanged sample lost 4% of its weight.
It is likely that the oleate ligand has been removed by decomposition in this region; it is also likely that some oleate ligand is still present in the fully exchanged sample, accounting for the small reduction in the mass of that sample in region C. That the exchanged sample loses less weight than the unexchanged sample may be ascribed to the large difference in molecular weights of the ligands, assuming the same number of ligands bond to a NC in each case. The TGA data suggest that a certain amount of octylamine ligand has been removed from the film during the annealing process at or above 190°C, allowing the MEH-PPV backbone chains closer contact with the nanocrystal surface. MEH-PPV has a much lower ionization potential (5 eV, close to the top valence band of bulk PbS) than octylamine (8.5 eV), forming a much lower barrier for holes in the nanocrystals. This would, lead to less effective or no confining effect on the holes, and thus a weaker quantum size effect. Hence, the energy gap of the nanocrystals is decreased as the valence band level approaches the bulk limit due to the reduced barrier height and resulting lack of hole confinement; this results in a less well-defined nanocrystal absorption peak (Figure 5(a) inset) and a red-shifted photocurrent spectrum (Figure 5(b)). Because of this decrease in hole confinement, photogenerated holes can move more freely from the nanocrystals to the polymer. This is consistent with the quenching of nanocrystal photoluminescence after annealing (Figure 5(b) inset). Also, the hole mobility is significantly increased, leading to the remarkable increases in the dark-, photo-and short circuit currents (Figure 6(b)).
Figures 9a to 9f shows cross-sectional TEM images at low (x 150K) and higher (x 500K) magnification for an unannealed sample (Figure 9a, b), ane samples annealed at 190°C (Figure 9 c,d) and 220°C (Figure 9 e, f). These images show a clear change in film morphology due to the annealing process.
No change in nanocrystal size after annealing is observed, however there is significant phase separation in the unannealed and 190°C annealed samples, as illustrated by the small, independent nanocrystal domains in Figures 9 a to d.
Although the spacing of nanocrystals within a domain does not appear to change, the separation of the nanocrystal domains is reduced by increasing the annealing temperature.
At different annealing temperatures, the polymer can move locally or on a larger scale, and will finally reside in the lowest energy configuration. The nanocrystals can diffuse and redistribute more easily in the polymer near or above its glass transition temperature 0215 °C), so that the separation between nanocrystal domains is reduced or eliminated. The more connected nanocrystal network, with reduced phase separation, would enhance electron hopping or tunnelling as electrons are less likely to become trapped at dead-ends in the network. Hence, electrons can move through the films more easily in samples annealed at higher temperature. It should be noted that the hopping or tunnelling current is reduced exponentially as the separation is increased. This is consistent with the exponential dependence of the dark current, photocurrent, and short circuit current on the annealing temperature(Fig. 6(b)).
The reason the photocurrent increases more quickly than the dark current is possibly due to the additional enhanced charge separation effect, caused by removal of the ligand barrier as discussed above. The faster time response of the photocurrent in the annealed samples (Figure 7), is likely due to the smaller barrier for holes and the improved electron transport properties that result after the thermal treatment.
In summary, ligand and film morphology control have a significant effect on the performance of PbS nanocrystal / MEH-PPV infrared-sensitive photovoltaic devices. Annealing appears to result in displacement of octylamine ligands from the NC surface, allowing more intimate contact with the MEH-PPV
phase, and thus improving the charge separation process. The quenching of the nanocrystal photoluminescence after annealing also suggests rapid exciton dissociation before recombination. Annealing also decreases the separation between isolated domains of nanocrystals within the network, enhancing the electron transport. This causes an increase in dark conductivity, and a relatively more stable and faster temporal response of the photoconductivity in devices made from the annealed samples, suggesting that the charge mobilities are enhanced. The combination of these changes in the ligand and film morphology caused by thermal annealing at 220°C dramatically improves the performance of the resulting devices, increasing the short circuit current by 200 times and the product of IS~ and V°~ by 600 times compared to the unannealed devices.
A
monochromatic power conversion efficiency of 0.001 % has been achieved.
Experimental Materials:
The synthesis of oleate-capped PbS nanocrystals followed that used in Ref. 13. These nanocrystals were then treated with octylamine in a ligand exchange procedure reported elsewhere. After the exhange process, the octylamine-capped nanocrystals were precipitated with N,N-dimethylformamide and redispersed in chloroform. The nanocrystal solutions were filtered using a 0.45 p.m filter. MEH-PPV was dispersed in chloroform by stirring overnight followed by two hours of ultrasonication and filtration through a 2 p,m filter. The nanocrystal and polymer solutions were then mixed to give an 80% weight fraction of nanocrystals relative to MEH-PPV.
Device fabrication:
In a typical procedure, a 170 nm thick polymer/nanocrystal blend film was spin-coated on to a 2.54 x 2.54 cm2 indium tin oxide (1T0) coated glass slide.
Films that were annealed were then heated on a hotplate at the designated temperatures for 1 hour in a N2-filled glove box with < 1 ppm residual oxygen and water. Finally, the upper contact (3 mm2) was deposited by vacuum evaporation forming a metal stack of 30 nm Mg/100 nm Ag/5 nm Au.
Characterization methods:
The dark current and photocurrent were measured using an Agilent 4155C
Semiconductor Parameter Analyzer and microprobe station. The optical excitation was provided by a 970 nm semiconductor laser working in CW mode with the beam enlarged to a diameter of ~ 3 mm by a lens. In the measurement of photocurrent spectral response and time response, no bias was applied to the devices and the load resistor. The resistance of the series load resistor was about three orders of magnitude smaller than the resistance of the device under illumination.
The potential drop across the load resistor was read by a lock-in amplifier (Model SR803 DSP) for the photocurrent spectral response and by a digital phosphor oscilloscope (Tektronix TDS5104) for the time response. To obtain the photocurrent spectrum, the light from a white light source was dispersed by a monochromater (Triax 320), and mechanically chopped at a frequency of 250 Hz.
The light intensity at each wavelength was separately measured so the photocurrent at each wavelength could be scaled to the same incident light intensity by assuming the photocurrent was linearly proportional to the light power in the low intensity region used.
Photoluminescence spectra were obtained using a Photon Technologies Inc. spectrofluorometer with a Samples for thermal gravimetric analysis (TGA) were precipitated from chloroform solution, isolated by centrifugation, and dried in vacuum for several hours prior to analysis. TGA was performed using a Cross-sectional TEM samples were prepared as follows: (1 ) a portion of the coated film was removed from the glass using a razor blade; (2) this film was glued onto a piece of plastic; (3) the plastic, with the sample attached, was microtomed to nm thick species and mounted the species onto the TEM grids.
The present invention uses nanotechnology to make plastic "see in the dark". The material of the present invention can be painted on walls, printed on paper - even sprayed on clothing. The devices made from the materials could be used in smart walls that sense the environment in a room; digital cameras that see in the dark; and clothing that turns the sun's power into electrical energy.

As used herein, the terms "comprises" and "comprising" are to be construed as being inclusive and opened rather than exclusive. Specifically, when used in this specification including the claims, the terms "comprises"
and "comprising" and variations thereof mean that the specified features, steps or components are included. The terms are not to be interpreted to exclude the presence of other features, steps or components.
It will be appreciated that the above description related to the invention by way of example only. Many variations on the invention will be obvious to those skilled in the art and such obvious variations are within the scope of the invention as described herein whether or not expressly described.
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Claims (53)

THEREFORE WHAT IS CLAIMED IS:

1. A nanocomposite layered device comprising:
a transparent substrate;
a hole conducting layer;
a semiconducting polymer layer; and a composite layer containing semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.

2. A nanocomposite layered device as claimed in claim 1 wherein the transparent substrate is chosen from a group consisting of quartz, glass and a transparent polymer.

3. A nanocomposite layered device as claimed in any one of claims 1 and 2 wherein the hole-conducting layer is one of a metal and pseudo-metallic material and wherein the hole-conducting layer is at least partially transparent

4. A nanocomposite layered device as claimed in claim 3 wherein the hole-conducting material is chosen from a group consisting of indium tin oxide, PEDOT:PSS and a thin transparent metal.

5. A nanocomposite layered device as claimed in any one of claims 1 to 4 wherein the semiconducting polymer layer is one of an inorganic and an organic material with a preference for hole conduction.

6. A nanocomposite layered device as claimed in any one of claims 1 to 5 wherein semiconducting polymer in the composite layer is one of a MEH-PPV and a regio-regular polythiophene.

7. A nanocomposite layered device as claimed in any one of claims 1 to 6 wherein the infrared-absorbing quantum dot nanoparticles in the composite layer are chosen from the group consisting of PbS, PbSe, InAs, InSb.

8. A nanocomposite layered device as claimed in claims 1 to 7 further including a metallic contact for electron extraction.

9. A nanocomposite layered device as claimed in claim 8 wherein the metallic contact is chosen from the group consisting of Mg, Al, and Ag.

10. A nanocomposite layered device as claimed in claim 9 wherein the metallic contact further includes an interlayer of an electro-rich material.

11. A nanocomposite layered device as claimed in claim 10 wherein the electro-rich material is Li.

12. A nanocomposite layered device as claimed in claim 8 wherein the metallic contact is generally a 3 square millimetre metal stack of 150nm Mg/100 nm Ag/ 10 nm Au.

13. A nanocomposite layered device as claimed in any one of claims 1 to 12 wherein the semiconducting layer is generally pin hole free.

14. A nanocomposite layered device as claimed in any one of claims 1 to 13 wherein the semiconducting polymer layer decreases the dark current.

15. A nanocomposite layered device as claimed in any one of claims 1 to 14 wherein semiconducting polymer layer allows a higher bias to be applied to the device.

16. A nanocomposite layered device as claimed in any one of claims 1 to 15 wherein the semiconducting polymer layer is of a thickness greater than 10 nm but less than 100 nm.

17. A nanocomposite layered device as claimed in any one of claims 1 to 16 wherein the ratio of the mass of the quantum dot particles to the semiconducting polymer in the composite layer is greater than 80% by mass.

18. A nanocomposite layered device as claimed in claim 17 wherein ratio of the mass of the quantum dot particles to the semiconducting polymer in the composite layer is 90% by mass

19. A process for producing a nanocystal composite layer comprising the steps of:
synthesizing quantum dot nanocrystals to produce nanocrystals capped with synthesized ligands;
exchanging the synthesized organic ligands with a new organic ligand to produce ligand-exchanged nanocrystals;
redispersing the ligand-exchanged nanocrystals in a solvent which is compatible with the solution-processing of the combined polymer-quantum dot dispersion to produce a prepared nanocrystal;
mixing prepared nanocrystals with the polymer matrix material in a predetermined percentage by weight to produce a nanocrystal composite layer.

20. A process as claimed in claim 19 wherein the solvents are chosen from a group consisting of chloroform, toluene, and pyridine.

21. A process as claimed in any one of claims 19 and 20 wherein the method of redispersion includes the steps of precipitation using a nonsolvent washing and redispersion.

22. A process as claimed in claim 21 wherein the nonsolvent is chosen form a group consisting of N,N-dimethylformamide, acetone, methanol, and isopropanol.

23. A process as claimed in any one of claims 19 and 20 wherein the method of redispersion includes the steps of evaporation of the previous solvent and redispersion in a new solvent

24. A process as claimed in claim 23 wherein the new solvent is chosen from a group consisting of chloroform and toluene.

25. A process as claimed in any one of claims 19 - 24 wherein the polymer matrix is MEH-PPV.

26. A process as claimed in any one of claims 19 - 25 wherein the nanocrystals capped with synthesized ligands were precipitated with a non-solvent chosen from the group consisting of methanol, isopropanol, and acetone, dried, and dispersed in an excess of a new ligand chosen from the group consisting of octylamine or butylamine..

27. A process as claimed in any one of claims 19 to 26 wherein in the synthesizing step nanocrystals is heated at a temperature between 30 and 70° C for a time ranging from 12 to 48 hours.

28. A process for producing a nanocomposite layered device comprising the steps of:
providing a transparent substrate;
coating the transparent substrate with a hole conducting layer to produce a coated substrate;
coating the coated substrate with a semiconducting polymer layer to produce a polymer coated substrate;
coating the polymer coated substrate with a infrared-absorbing quantum dot nanoparticle layer to produce a nanocomposite layered device.

29. A process as claimed in claim 28 wherein the nanoparticle layer is a composite layer containing semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.

30. A process as claimed in any one of claims 28 and 29 wherein the semiconducting polymer is one of MEH-PPV and regio-regular polythiophenes.

31. A process as claimed in any one of claims 28 to 30 wherein the substrate is one of glass, quartz, and a transparent polymer.

32. A process as claimed in any one of claims 28 to 31 wherein the hole conducting layer is chosen from the group consisting of indium tin oxide, PEDOT:PPS and a thin transparent layer.

33. A process as claimed in any one of claims 28 to 32 wherein the infrared -absorbing quantum dot nanoparticles are chosen from the group consisting of PbS, PbSe, InAs, InSb.

34. A process as claimed in any one of claims claim 28 to 33 further including the step of depositing an electrical contact on the nanocrsytal layered device.

35. A process as claimed in any one of claims 28 to 34 wherein nanocomposite layered device has a smeiconducting polymer layer which is has a thickness that is greater than 10nm and less than 100nm.

36. A process as claimed in any one of claims 28 - 35 wherein first coating step is spin coating and then the coated substrate is annealed at between 150 and 250°C for between 30 minutes and five hours.

37. A process as claimed in any one of claims 28 - 35 wherein first coating step is spin coating and then the coated substrate is annealed at between 180 and 220°C for between two and four hours.

38. A process as claimed in any one of claims 28 -37 wherein the nanocomposite layered device includes a nanocomposite layer that is of a thickness such that significant absorption of light is achieved where the distance between contact and the average nanocrystal is less than the transport length of each type of charge carrier.

39. a process as claimed in claim 38 wherein the nanocomposite layer is greater than 30 nm and the transport length of each type of charge carrier is between 100-150 nm.

40. A process as claimed in claim 28 - 39 wherein the second coating step comprising the steps of:
synthesizing quantum dot nanocrystals to produse nanocrystals capped with synthesized ligands;
exchanging the synthesized organic ligands with a new organic ligand to produce ligand-exchanged nanocrystals;
redispersing the ligand-exchanged nanocrystals in a solvent which is compatible with the solution-processing of the combined polymer-quantum dot dispersion to produce a prepared nanocrystal;
mixing prepared nanocrystals with the polymer matrix material in a predetermined percentage by weight to produce a nanocrystal composite layer.

41. A process as claimed in claim 40 wherein the solvents are chosen from a group consisting of chloroform, toluene, and pyridine.

42. A process as claimed in any one of claims 40 and 41 wherein the method of redispersion includes the steps of precipitation using a nonsolvent washing and redispersion.

43. A process as claimed in claim 42 wherein the nonsolvent is chosen form a group consisting of N,N-dimethylformamide, acetone, methanol, and isopropanol.

44. A process as claimed in any one of claims 40 and 41 wherein the method of redispersion includes the steps of evaporation of the previous solvent and redispersion in a new solvent

45. A process as claimed in claim 44 wherein the new solvent is chosen from a group consisting of chloroform and toluene.

46. A process as claimed in any one of claims 40 to 45 wherein the polymer matrix is MEH-PPV.

47. A process as claimed in any one of claims 40 to 46 wherein the nanocrystals capped with synthesized ligands were precipitated with a non-solvent chosen from the group consisting of methanol, isopropanol, and acetone, dried, and dispersed in an excess of a new ligand chosen from the group consisting of octylamine or butylamine..

48. A process as claimed in any one of claims 40 to 47 wherein in the synthesizing step nanocrystals were heated at a temperature between 30 and 70° C for a time ranging from 12 to 48 hours.

49. A nanocomposite layered device comprising:
a transparent substrate;
a hole conducting layer;
a semiconducting polymer layer; and a infrared-absorbing quantum dot nanoparticle layer.

50. A nanocomposite layered device as claimed in claim 49 wherein the infrared-absorbing quantum dot nanoparticle layer is a composite layer containing semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.

51. A nanocomposite comprising a semiconducting polymer in combination with infrared-absorbing quantum dot nanoparticles.

52. A nanocomposite as claimed in claim 51 wherein semiconducting polymer is one of a MEH-PPV and a regio-regular polythiophene.

53. A nanocomposite layered device as claimed in any one of claims 51 and 52 wherein the infrared-absorbing quantum dot nanoparticles in the composite layer are chosen from the group consisting of PbS, PbSe, InAs, InSb.