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oastm_03
Aerosol-assisted Chemical Vapour Deposition (AACVD) is a widely used thin film preparation.
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oastm_03
train1
semi
oastm_03
The technique involves the transport of precursors within a vapourised solvent over a heated substrate, whereby the precursors effect thin film formation [6-8].
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oastm_03
train1
semi
oastm_03
Doped-SnO2 formation in AACVD requires the presence of tin, oxygen and dopant sources, delivered either together within the same solution or from separate solutions.
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oastm_03
train1
semi
oastm_03
It has been found that the choice of precursor components and reactions prior to deposition have a marked effect on the resultant TCO properties [9].
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oastm_03
train1
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oastm_03
FTO and other doped-SnO2 materials have also been deposited using atmospheric-pressure CVD (APCVD), spray pyrolysis, sol-gel dip coating and sputtering [5,10-12].
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oastm_03
train1
semi
oastm_03
The aim of this paper is thus to investigate the effects of halide dopants on the TCO properties of SnO2.
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oastm_03
train1
semi
oastm_03
Furthermore, the effects of these dopants on the general precursor chemistry will also be investigated.
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oastm_03
train1
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oastm_03
The results reinforce the position of fluorine as the best dopant and yield insight into the interaction between precursor components prior to thin film deposition; namely that of a halide exchange reaction.
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oastm_03
train1
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oastm_03
Experimental details
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oastm_03
train1
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oastm_03
All chemicals were used as bought; butyltintrichloride (95%; Sigma-Aldrich), potassium fluoride (98%; Aldrich), potassium chloride (99.5%; Analar), potassium bromide (99+ %; Aldrich), potassium iodide (99.8%; Analar), and propan-2-ol (Merck).
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oastm_03
train1
semi
oastm_03
Filtered compressed air was obtained through a house line.
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oastm_03
train1
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oastm_03
Deposition was carried out on 3.2mm thick plain soda-lime silica float glass with a 50nm thick SiO2 barrier layer, as supplied by Pilkington NSG.
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oastm_03
train1
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oastm_03
All substrates were pre-washed with soaped water, propan-2-ol and acetone then dried in air prior to loading into the reactor.
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oastm_03
train1
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oastm_03
Synthesis
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oastm_03
train1
semi
oastm_03
The single-source AACVD FTO precursor was made by mixing butyltin trichloride (MBTC; 0.2moldm-3), potassium halide (KX; where X=F, Cl, Br or I) (6wt.%-X) and propan-2-ol.
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oastm_03
train1
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oastm_03
The mixture was stirred for 12h then filtered prior to deposition to remove the precipitate.
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oastm_03
train1
semi
oastm_03
The AACVD was carried out in a flat-bed, cold-walled tubular reactor, as described elsewhere [6,13].
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oastm_03
train1
semi
oastm_03
A thermocouple controlled carbon block heater maintained substrate temperatures.
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oastm_03
train1
semi
oastm_03
Depositions were carried out on Pilkington silica-coated barrier glass in order to prevent the leaching of ions from the glass into the thin film.
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oastm_03
train1
semi
oastm_03
A second piece of float glass was suspended 8mm above the substrate, silica-side down in order to ensure a laminar flow of the gas/aerosol.
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oastm_03
train1
semi
oastm_03
Films were deposited at 450°C with substrates heated to the desired temperature before deposition and cooled in air ambient in the reactor after deposition.
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oastm_03
train1
semi
oastm_03
AACVD was carried out using the pneumatic aerosol generation method employing a TSI Model 3076 Constant Output Atomiser utilising filtered, compressed air carrier gas operating at constant 200kPa pressure.
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oastm_03
train1
semi
oastm_03
Deposition times were kept constant at 30min.
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oastm_03
train1
semi
oastm_03
Analysis
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oastm_03
train1
semi
oastm_03
X-ray diffraction (XRD) measurements were made on a Bruker GADDS D8 diffractometer in a glancing angle configuration using a Cu-Kα X-ray source.
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oastm_03
train1
semi
oastm_03
Readings were taken over a 2θ range of 10-66°.
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oastm_03
train1
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oastm_03
Diffraction patterns were analysed for crystallinity, orientation, phase purity and crystallite size against a corundum (Al2O3) standard.
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oastm_03
train1
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oastm_03
Powder XRD (PXRD) measurements of precipitates were made on a Bruker D4 flat plate powder x-ray diffractometer using a Cu-Kα X-ray source over the 15-70° 2 θ range.
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oastm_03
train1
semi
oastm_03
Raman spectroscopy measurements were carried out on a Renishaw 1000 invia UV-visible spectrometer under ambient conditions.
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oastm_03
train1
semi
oastm_03
A 514.5nm laser source was used to probe the film over the 100-1100cm-1 wavenumber range.
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oastm_03
train1
semi
oastm_03
Scanning electron microscopy (SEM) images were obtained using a JEOL JSM-6301F Field Emission SEM at a 5keV accelerating voltage.
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MEASUREMENT
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oastm_03
train1
semi
oastm_03
Samples were coated with gold prior to deposition.
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6,525
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oastm_03
train1
semi
oastm_03
Images were examined to determine the surface morphology and grain growth characteristics.
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6,616
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oastm_03
train1
semi
oastm_03
Room temperature Transmittance-Reflectance (T-R) profiles were taken using a Perkin Elmer Fourier Transform Lambda 950 UV-visible spectrophotometer over a 250-3000nm wavelength range against an air background.
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oastm_03
train1
semi
oastm_03
Film thickness measurements were carried out on a Filmetrics F20 analyser in against an as-supplied FTO reference.
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oastm_03
train1
semi
oastm_03
Room temperature Hall Effect measurements were carried out on an Ecopia HMS-3000 in the Van der Pauw configuration.
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oastm_03
train1
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oastm_03
Measurements were taken using a 0.58T permanent magnet and a current of 0.1μA.
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oastm_03
train1
semi
oastm_03
Tests were carried out on samples cut to squares measuring ≈1×1cm.
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oastm_03
train1
semi
oastm_03
Silver paint (Agar Scientific) was used to form ohmic contacts, the integrity of which was tested prior to measurement.
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oastm_03
train1
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oastm_03
The Hall Effect method was used to find the resistivity, charge carrier mobility and charge carrier density.
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oastm_03
train1
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oastm_03
Results and discussion
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oastm_03
train1
semi
oastm_03
Halide-doped tin oxide films of fluorine-tin-oxide (F-TO), chlorine-tin-oxide (Cl-TO), bromine-tin-oxide (Br-TO) and iodine-tin-oxide (I-TO) were synthesised.
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oastm_03
train1
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oastm_03
The as-deposited films were adherent, transparent and could be readily replicated.
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oastm_03
train1
semi
oastm_03
Film deposition occurred on the bottom plate of glass inside the reactor.
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oastm_03
train1
semi
oastm_03
The films were adherent, passing the scotch tape test and were impervious to common solvents.
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oastm_03
train1
semi
oastm_03
However, they could be marked with a brass pen.
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oastm_03
train1
semi
oastm_03
The XRD spectra of films obtained under the different regimes are shown in Fig. 1.
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oastm_03
train1
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oastm_03
Texture coefficient values quantifying changes in preferred orientation and estimated Scherrer crystallite sizes are noted in Table 1.
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oastm_03
train1
semi
oastm_03
The sub-micrometre film thicknesses meant that a slight broad hump was visible at low 2θ angles; due to diffraction from the amorphous glass substrate.
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oastm_03
train1
semi
oastm_03
In all cases films exhibit the well-known tetragonal cassiterite structure of SnO2, with near phase-pure polycrystalline films obtained [1,14].
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oastm_03
train1
semi
oastm_03
The sole anomalous peak found at 31° is attributed to the persistent kinetic SnO(101) phase of tin oxide which seemed to increase in intensity with halide size, indicating a greater presence of mixed tin oxide phases.
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oastm_03
train1
semi
oastm_03
This implies that the halide dopants act as a kinetic obstruction to the formation of SnO2; the effects amplified with increasing halide size.
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oastm_03
train1
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oastm_03
For all doped films, there is a strong preferred orientation along the (211) direction, as demonstrated by texture coefficient calculations; larger values indicating greater directionality [6,15].
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oastm_03
train1
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oastm_03
This plane is thought to have the most stable thin film orientation and so is favoured during initial film formation, with low growth rates and with increasing film thickness [16-18].
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oastm_03
train1
semi
oastm_03
Scherrer crystallite size calculations [19] (see Table 1) show that all dopants produce films with average crystallite sizes of the order of nanometre dimensions.
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oastm_03
train1
semi
oastm_03
Values also indicate doping with fluorine results in smaller average crystallites as compared to the other halide dopants.
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oastm_03
train1
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However, larger halide doping did not cause further increases in average crystallite size.
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oastm_03
train1
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oastm_03
The collated Raman spectra for the doped films are displayed in Fig. 2 along with a powder SnO2 reference.
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oastm_03
train1
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All vibrations conform to the expected SnO2 A1g, B2g and Eg reference peaks, indicating the predominance and integrity of the SnO2 structure.
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oastm_03
train1
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oastm_03
The lack of differences between spectra may indicate the minimal incorporation of dopants within the structure.
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oastm_03
train1
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oastm_03
However, given the low intensity of Raman patterns produced from thin film samples it was difficult to compare peak shifts and broadenings that are associated with doping.
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oastm_03
train1
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oastm_03
The broadened nature of the peaks is due to both the thin film nature and nanocrystalline dimensions of the products [20].
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oastm_03
train1
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oastm_03
The greater broadening observed for the Eg band, which is thought to be sensitive to singly ionised oxygen vacancies, is attributed to film non-stoichiometry [21].
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oastm_03
train1
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oastm_03
The nanocrystalline properties of the films are evidenced by both the broad SnO2 grain surface vibration band at ≈570cm-1 and the peak at ≈250cm-1, reinforcing calculated crystallite values [22,23].
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oastm_03
train1
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oastm_03
Top-down SEM images of the different doped samples are shown in Fig. 3 below along with an undoped SnO2 thin film sample.
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oastm_03
train1
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oastm_03
The images show the crystalline nature of the films as indicated by XRD.
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oastm_03
train1
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oastm_03
The microstructure is polycrystalline with continuous grain distributions of varying sizes.
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oastm_03
train1
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oastm_03
The well-known facetted structure of doped tin oxide thin films is again observed and is indicative of a surface-nucleated thin film growth process [6,24,25].
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oastm_03
train1
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oastm_03
The images indicate that all the halides induce marked morphological changes upon doping.
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11,012
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['Results']
QUAL_MEASUREMENT
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oastm_03
train1
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oastm_03
Average grain sizes seem to reflect the relationship as found for average crystallite size; FTO grains being smaller than those of other halide dopants between which there is little difference.
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['Conclusion']
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oastm_03
train1
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oastm_03
In all cases, preparation of the single-source precursor formed a precipitate that was filtered from the precursor mixture prior to deposition.
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oastm_03
train1
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oastm_03
Regardless of the dopant salt added, analysis of the precipitates indicated the presence of appreciable quantities of potassium chloride, KCl, although small amounts of the original potassium salt were also identified in certain cases (see Fig. 4).
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oastm_03
train1
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oastm_03
This indicates a potential halide-exchange mechanism between the halide from the salt (KX) and a chlorine atom from the MBTC precursor.
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['Explanation']
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oastm_03
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oastm_03
This postulated exchange may be a marker towards higher-performing films [26].
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oastm_03
train1
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oastm_03
The halide exchange occurred despite the hard-bonding nature of the potassium halide salts and their poor solubility in the propan-2-ol carrier solvents, thus indicating the favourability of this process.
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['Results']
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oastm_03
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oastm_03
The fact that this exchange seems to have occurred at a Sn-Cl MBTC bond rather than the weaker SnC bond is notable.
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12,109
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We have also observed the same exchange process with ammonium halide salts.
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Hall Effect measurements identified all films as n-type semiconductors.
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Charge carrier concentration, mobility and resistivities are listed in Table 1.
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oastm_03
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The effects of the dopants were clear, with far higher charge carrier concentration, (N), than those found for undoped SnO2 thin films (1017-19cm-3 range) [1,2,5].
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Films also show reasonably good charge carrier mobility, (μ), values, which may be constricted due to the high charge carrier concentration values obtained.
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The characteristic antagonistic nature between N and μ is observed; the optimisation of this trade-off being extremely important for functional applications [27].
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The N and μ values combine to yield the resistivity, ρ, and sheet resistance, Rsheet (a commonly used thin film measurement), values.
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These compare favourably with current commercial standards [6].
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oastm_03
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Fluorine is found to be the most effective dopant in terms of charge carrier generation resulting in the lowest ρ and Rsheet values of the set.
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oastm_03
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The effect of differences between other halide dopants on electrical performance is less marked, as evidenced by their similar electrical conductivity properties.
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Fig. 5 gives the optical characteristics of the doped-SnO2 films.
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oastm_03
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The transmittance-reflectance profiles for all the films show good optical transmittance properties in the visible range, with transparencies in the region of 80% making them suitable for most functional applications, which require a minimum 75% transmittance level [5].
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The characteristic IR-reflectance characteristics of doped SnO2 films as caused by the presence of a large concentration of charge carriers are also observed [28].
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The fluorine-doped SnO2 thin film demonstrates the highest energy plasmon absorption edge attributed to its superior charge carrier generation (see Table 1).
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Whilst the effects of the fluorine dopant are clear, the differences between the alternative halide-doped SnO2 thin films are quite marginal, however there is seemingly a trend for an increased red-shift in the plasmon absorption edge with increasing halide size.
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Optical bandgap, Eopt, values were calculated using the TAUC method; extrapolating the linear section of an (ahυ)2 vs E/eV plot (see Table 1) [29].
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All bandgaps were larger than the reported 3.6eV value for bulk SnO2.
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This indicated the extensive presence of dopant donor levels, corroborating the large charge carrier concentration values seen in Hall Effect measurements.
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oastm_03
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oastm_03
This effect resulted in a Moss-Burstein blue-shift of the bandgap to higher values [5].
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The Eopt values highlight the effectiveness of all the halides as useful dopants for SnO2-based TCOs, correlating with the large N-values.
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oastm_03
However, the differences between the dopant-induced Eopt values are less clear-cut.
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14,966
15,049
['Results']
QUAL_MEASUREMENT
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oastm_03
train1
semi
oastm_03
The Urbach tail refers to the sub-bandgap relationship between the absorption coefficient and photon energy [30].
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15,050
15,163
['Background', 'Background_PriorWork']
O
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oastm_03
train1
semi
oastm_03
The value, as given by Eu, is an indicator of the degree of disorder induced by the thermal and structural defects which cause the density of states to extend into the bandgap.
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15,164
15,340
['Background']
O
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oastm_03
train1
semi
oastm_03
The greater the width of the tail, the greater is the degree of disorder [31].
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15,341
15,419
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O
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oastm_03
train1
semi