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The electronic properties of hydrogenated nanocrystalline silicon (nc-Si:H) were studied using drive-level capacitance profiling (DLCP) to obtain defect density profiles as well as transient photocapacitance (TPC) and transient photocurrent (TPI) spectroscopies to study the spectra of defect related optical transitions. These measurements were performed on a series of n–i–p solar cell devices with intrinsic layer thickness of roughly 1 μm. The nc-Si:H intrinsic layers were deposited using RF or MVHF glow discharge with various hydrogen dilution profiles predominantly on specular stainless steel substrates (SS/n + /i nc-Si:H/p + /ITO), but also on textured back reflectors (SS/Ag/ZnO/n + /i nc-Si:H/p + /ITO) in some cases. Crystallite fractions were estimated using Raman spectroscopy. The electronic properties determined by our measurements could be correlated with variations in structural device parameters and with the degree of hydrogen dilution profiling during growth. We also found, depending on the growth conditions, that the devices exhibited markedly different behaviors after prolonged light exposure (100 h using light at 610 nm and 500 mW/cm 2 intensity). We discuss one specific microscopic mechanism that may be responsible for the light-induced changes that we have observed.

A particulate precursor of superconductive Bi2Sr2CaCu2 oxide dispersed in an aqueous poly(vinyl alcohol) solution, was shaped into fibres. The fibres fired at a Tmax of 850 °C were very porous. Although they exhibited a Meissner on-set transition at 85 K, electrical resistance at 0.02 Acm−2 at 77 K was still not zero. Exposing the porous fibres to a temperature slightly above their melting point densified them. The treated fibres had a sharp Meissner transition and could carry critical current (Jc) as high as 331 A cm−2 at 77 K. They were also more resistant to the effect of a magnetic field than the fibre fired at 850 °C. Eighty percent of the treated fibre was found to be the superconductive 2 2 1 2 phase.

The effect of trace carbon impurities on the density of states in amorphous silicon has been studied. The deep-defect densities and mobility-gap electronic structure were characterized with electron-spin resonance, drive-level capacitance profiling, and transient photocurrent measurements. Good quantitative agreement in the defect densities deduced from these three methods has been found. This implies a ratio between charged and neutral dangling bonds of at most 2 to 1. Light-induced changes in the mobility-gap electronic structure were also investigated in these films. A small but significant increase in the density of light-induced defects was observed for samples with carbon impurities at the 1 at. % level. The time to saturation of the light-induced degradation for the carbon containing samples was also significantly increased. We discuss the interpretation of these results in terms of two possible mechanisms: either from the presence of carbon-related precursor sites, or by widening of the band gap with carbon alloying.

High-hydrogen-diluted films of hydrogenated amorphous Si (a-Si:H) 0.5 μm in thickness and optimized for solar cell efficiency and stability, are found to be partially microcrystalline (μc) if deposited directly on stainless steel (SS) substrates but are fully amorphous if a thin n layer of a-Si:H or μc-Si:H is first deposited on the SS. In these latter cases, partial microcrystallinity develops as the films are grown thicker (1.5–2.5 μm) and this is accompanied by sharp drops in solar cell open circuit voltage. For the fully amorphous films, x-ray diffraction (XRD) shows improved medium-range order compared to undiluted films and this correlates with better light stability. Capacitance profiling shows a decrease in deep defect density as growth proceeds further from the substrate, consistent with the XRD evidence of improved order for thicker films.

This report summarizes the development and evaluation of higher-bandgap absorbers in the CIS alloy system. The major effort focused on exploring suitable absorbers with significant sulfur alloying in collaboration with Shafarman's group at the Institute of Energy Conversion. Three series of samples were examined; first, a series of quaternary CuIn(SeS)2-based devices without Ga; second, a series of devices with pentenary Cu(InGa)(SeS)2 absorbers in which the Se-to-S and In-to-Ga ratios were chosen to keep the bandgap nearly constant, near 1.52 eV. Third, based on the most-promising samples in those two series, we examined a series of devices with pentenary Cu(InGa)(SeS)2 absorbers with roughly 25 at.% S/(Se+S) ratios and varying Ga fractions. We also characterized electronic properties of several wide-bandgap CuGaSe2 devices from both IEC and NREL. The electronic properties of these absorbers were examined using admittance spectroscopy, drive-level capacitance profiling, transient photocapacitance, and transient photocurrent optical spectroscopies. The sample devices whose absorbers had Ga fraction below 40 at.% and S fractions above 20 at.% but below 40% exhibited the best electronic properties and device performance.

We have used sustained light-soaking in the near-infrared (780 nm wavelength) to modify the properties of the absorber layer in CIGS solar cells, and thus study the relationship between the absorber electronic properties and the device performance. Through this light-soaking treatment we can increase the hole carrier density in the CIGS absorber, as well as the density of the commonly observed 0.3 eV bulk deep acceptor, by up to a factor of 5. The device performance was periodically recorded under the same 780 nm light, and was found to degrade due to a reduction in fill factor and short circuit current. We demonstrate that these changes can be largely attributed to a reduction in the photogenerated carrier collection, due to a decrease in the depletion width. Based on these data, we estimate the minority carrier diffusion length to be about 0.2 ?m. At the same time, no change in open circuit voltage was observed, indicating that the recombination rate through the dominant recombination channel remained nearly constant. This means that it cannot be the 0.3 eV bulk defect. Detailed SCAPS modeling was carried out and reinforces this conclusion.

We have used electronic and optical techniques to characterize alloys of the Cu(In,Ga)(S,Se)2 material system. The alloys were prepared such that the bandgap of the resultant materials was near 1.5 eV. These materials are interesting as the absorber layer of thin-film solar cell devices, and were studied in a solar cell device configuration. Electronic characterization techniques included admittance spectroscopy and drive-level capacitance profiling (DLCP). Optical techniques included transient-photocapacitance and transient-photocurrent spectroscopies. From these measurements we were able to determine defect activation energies and profiles, Urbach energies, and information about deeper (optical) defect positions and widths. These data are used to suggest a model of a deep electron trap 200 meV to 300 meV below the conduction band that is filled optically and emptied thermally, and may affect solar cell device performance.

The electronic properties of working nanocrystalline silicon (nc-Si:H) solar cell devices with conversion efficiencies up to 8.6% were studied using junction capacitance methods. The set of devices examined were deposited on both specular stainless steel substrates and Ag/ZnO textured back reflectors. These devices included nc-Si:H grown under constant H2 dilution, and also with profiled H2 dilution to control the crystallite sizes and volume fraction. Transient photocapacitance and transient photocurrent spectroscopies were used to obtain sub-band-gap optical spectra. A comparison of these two kinds of spectra also allowed us to deduce the minority carrier collection fractions as a function of temperature and light-induced degradation. Light-soaking was found to cause a distinct decrease in minority carrier collection, as well as a consistent decrease in defects responding to drive-level capacitance profiling. A tentative microscopic model is proposed that accounts for these degradation effects in nc-Si:H.

Voltage-pulse stimulated capacitance transient measurements on a series a-Si:H/a-Si, Ge:H devices disclose a large density of hole traps at or very close to the heterojunction interface. The transient signal magnitude is independent of temperature or applied bias, ruling out charge polarization effects or a defect creation process caused by the filling pulse. While the areal density of such hole traps is considerable (within a factor of 2 of 1011 cm−2 for all samples) these traps do not appear to behave as recombination centers. Also, the treatment of the a-Si:H/a-Si,Ge:H interface during growth can significantly alter the concentration of these traps.

A major effort during this subcontract period has been to evaluate the microcrystalline Si material under development at United Solar Ovonics Corporation (USOC). This material is actually a hydrogenated nanocrystalline form of Si and it will be denoted in this report as nc-Si:H. Second, we continued our studies of the BP Solar high-growth samples. Third, we evaluated amorphous silicon-germanium alloys produced by the hot-wire chemical vapor deposition growth process. This method holds some potential for higher deposition rate Ge alloy materials with good electronic properties. In addition to these three major focus areas, we examined a couple of amorphous germanium (a-Ge:H) samples produced by the ECR method at Iowa State University. Our studies of the electron cyclotron resonance a-Ge:H indicated that the Iowa State a Ge:H material had quite superior electronic properties, both in terms of the drive-level capacitance profiling deduced defect densities, and the transient photocapacitance deduced Urbach energies. Also, we characterized several United Solar a Si:H samples deposited very close to the microcrystalline phase transition. These samples exhibited good electronic properties, with midgap defect densities slightly less than 1 x 1016 cm-3 in the fully light-degraded state.

We report the deposition of improved hydrogenated amorphous silicon germanium (a-SiGe:H) films by the hot wire CVD (HWCVD) technique using a tantalum filament operating at a low temperature. We gauge the material quality of the a-SiGe:H films by comparing infrared, small angle X-ray scattering (SAXS), photocapacitance and conductivity measurements to earlier results, and fabricate single junction n-i-p solar cell devices using these i-layers.

The electronic properties of hydrogenated nanocrystalline silicon (nc-Si:H) were studied using junction capacitance methods. Drive-level capacitance profiling (DLCP) measurements revealed significant differences for nc-Si:H layers deposited under constant hydrogen dilution compared to those deposited using hydrogen profiling, with lower DLCP densities in the latter case. Transient photocapacitance (TPC) measurements revealed the mixed-phase nature of these materials. It disclosed spectra that appeared quite microcrystalline-like at lower temperatures, but more similar to a-Si:H at higher temperatures where the minority carrier collection is higher in the nanocrystalline component of these samples. This then suppresses the TPC signal from this component compared to the a-Si:H component. In contrast, because transient photocurrent signals are enhanced by the additional minority carrier collection, those spectra appear microcrystalline like at all temperatures. We also investigated the effects of light-induced degradation in these devices. This caused a dramatic decrease in hole collection, similar to that caused by reducing the measurement temperature of the samples. However, the light exposure did not appear to increase the deep defect density (dangling bonds).

Sub-bandgap defect densities and minority carrier collection properties have been characterized for a series of CuIn/sub 1-x/Ga/sub x/Se/sub 2/ devices with varying device efficiencies. Samples fabricated using reduced substrate temperatures during growth have also been studied, and show additional defect response. Transient photocapacitance and photocurrent spectroscopies were employed to deduce the defect distributions and minority carrier mobilities. Drive-level capacitance profiling was used to determine the spatial and thermal energy distributions of the majority carrier traps. Photovoltaic device parameters were determined for all samples. It appears that the device efficiency is not clearly controlled by any single sub-bandgap defect population.

This report describes our experimental studies which have been concentrated in roughly five areas. Specifically: (1) We have examined a?Si:H grown very close to the microcrystalline phase boundary, so-called''edge material,'' to help understand why such material is more stable with respect to light-induced degradation; (2) We have also studied the electronic properties, and degradation characteristics of mixed phase material that is mostly a?Si:H, but which contains a significant microcrystalline component; (3) We have examined the electronic properties of high deposition rate material. These studies have included both moderately high deposition rate material (up to 6/s) produced by the PECVD growth method, and extremely high deposition rate material (up to 130/s) produced by the HWCVD growth method. (4) We have examined series of a-Si,Ge:H alloys from several sources. In one extensive series of studies we examined low Ge fraction alloys in an attempt to learn more about the fundamentals of degradation in general. In a couple other studies we evaluated the properties of a-Si,Ge:H alloys produced by methods we had not previously examined. (5) Finally, for three different types of samples we compared basic material properties with companion cell performance data. This was carried out in each case on series of samples for which one or more specific deposition parameters were varied systematically.

An overriding theme of the work described in this report has been the effect of partial crystallinity, or the approach to partial crystallinity, on the electronic properties of a-Si:H. This includes, of course, how degradation or the relative stability of these films is affected by the approach to, or onset of, microcrystallinity. The authors first discussed the results on a set of samples produced by dc reactive magnetron sputtering, obtained in collaboration with John Abelson's group at the University of Illinois, for which they demonstrated the existence of a small, but significant, microcrystalline component. For these films, the degradation kinetics was found to be quite unusual; however, it could be well accounted for by a model that postulated two phases of degrading material. One was a-Si:H host material of good quality and the other was a more defective component associated with boundary regions near the microcrystallites. The sub-band-gap photocapacitance measurements on these films also indicated the existence of a distinct feature (a ``shoulder'' with a threshold near 1.1 eV) that signaled the presence of the microcrystalline phase. The second set of samples investigated were produced by Uni-Solar, deposited under conditions of high hydrogen dilution, very close to but just below the microcrystalline phase boundary. Here they found that the defect density following light-induced degradation decreased as the film thickness increased. Corroborating their findings with X-ray diffraction results obtained by Don Williamson on sets of similar films, the authors concluded that the films were becoming more ordered and less defective just prior to the onset of a detectable microcrystalline component. Furthermore, they found that at almost exactly the conditions that Williamson found XRD evidence for the onset of microcrystallinity, they found the appearance of the distinctive ``shoulder'' in the sub-band-gap photocapacitance spectra. Third, they investigated two sets of samples where the deposition rate had been varied to include samples grown at moderate to high rates. In one set of samples, produced at ETL, samples deposited under H{sub 2} dilution were found to exhibit extremely low deep defect densities and narrow Urbach tails, indicating films of exceptional quality. The photocapacitance spectra for these films were found to contain evidence for a small degree of microcrystallinity. In another set of samples, produced at UniSolar, they found evidence for increasing defect densities plus somewhat larger Urbach energies for the films deposited at higher rates. This is consistent with the fact that the photovoltaic device performance is significantly poorer for the higher deposition rate material. Finally, they discussed the general issue of deep defect densities in the a-Si,Ge:H alloys. They again demonstrated how well the deep defect densities in such samples from several sources could be fit using the spontaneous bond-breaking model of Martin Stutzmann. This implies that such state-of-the-art alloy films have been optimized in a quantifiable sense. They also found that the increase in deep defect density with small amounts of P and B dopants could also be reproduced reasonably well by modifying the spontaneous bond-breaking model to include the extra energy terms associated with charged defects.

The work carried out by the University of Oregon Under this subcontract focused on the characterization and evaluation of low-gap (a-Si,Ge:H) alloy materials and on issues related to overall stability in the mid-gap (a-SiH) materials. First, researchers characterized an extensive series of Uni-Solar a-Si,Ge:H samples using drive-level capacitance profiling and the analysis of sub-band-gap photocapacitance and photocurrent spectra. Thus, several bands of deep defect transitions were identified. Researchers were able to verify that charged defects are responsible for the different observed defect bands in device-quality a-Si,Ge:H alloy material. Second, they reported results of their measurements on a-Si,Ge:H alloy ''cathodic'' samples produced at Harvard University; these samples were found to exhibit significantly lower defect densities in the high Ge composition range (>50at.% Ge) than alloy samples produced either by conventional glow discharge of photo-chemical vapor deposition. Third, they performed voltage pulse stimulated capacitance transient measurements on a-Si:H/a-Si,Ge:H heterostructure samples to look for carrier trapping states that might be associated with this interface; they found there was a clear signature of trapped hole emission extending over long times associated specifically with the interface itself in concentrations of roughly 10{sup 11} cm{sup -2}. Fourth, researchers reported the results on several hot-wire a-Si:H samples produced with varying hydrogen levels. Their studies indicate that hot-wire-produced a-Si:H, with H levels between 2-5at.%, should lead to mid-gap devices with superior properties. Finally, they discussed some results on glow-discharge material, as well electron-cyclotron-resonance-deposited a-Si:H grown under hydrogen dilution conditions, and confirmed that, in terms of deep-defect creation, such films exhibited improved stability compared to conventional glow-discharge material.

We report the results of junction capacitance measurements on thin tetrahedral amorphous carbon (ta-C) films to deduce their defect densities. We find defect densities in the range 3 - 7 × 1017 cm−3 in the undoped ta-C films, and roughly an order of magnitude larger in the nitrogen doped (n-type) films. In some cases fairly uniform defect profiles were obtained covering a thickness of a couple of hundreds angstroems. We also observed a thermal activation process of carriers from defect states at the ta-C/c-Si interface with an activation energy in the range of 0.4eV to 0.5eV.

We review the progress of the teamed amorphous silicon research activities sponsored by NREL Thin-Film Partnership and by EPRI. We summarize the technical progress made since the last published report and attempt to assess the operational efficiency of the teams and the value of teaming.

We have applied the Drive-Level Capacitance Profiling (DLCP) method to n-i-p a-Si:H diodes to characterize the mid-gap defect densities in the i layer. Our results show that there are no significant changes in the drive-level densities, Ndl, in n-i-p diodes and p+-i-m as well as n-i-m Schottky diodes, which indicates that DLCP can directly provide reliable energy distribution and spatial distribution of the mid-gap defects in the n-i-p device. We have found that the ratio of Ndl to ND*, the ionized defect density determined by hole onset measurement, is changed with the deposition conditions; it is 3 for standard samples, 2 for helium diluted samples and 6 for hydrogen diluted samples. These results indicate that there may be different defect distributions in these materials, which suggest the ratio of charged (D-) density to the neutral defect (D0) density may be altered when growth conditions are varied.

Significant progress has been made in the area of multi-junction solar cells and stabilized efficiencies of 11.2% and 10.2% have been reported for small-area cells and large-area panels, respectively. The authors have performed voltage-pulse stimulated capacitance transient measurements along with other junction capacitance measurements on a-Si:H/a-Si,Ge:H heterostructures deposited on p-type crystalline silicon using the glow discharge technique. For a filling pulse that puts the c-Si/a-Si:H junction in forward bias, the capacitance transients consist of two components--a fast component corresponding to electron emission and a slow component corresponding to hole emission. For a fixed starting reverse bias, they have found that the density of trapped holes is proportional to the product of the filling pulse voltage and the filling pulse width and reaches a saturation value at a certain value of the product. These hole traps appear to reside at or very close to the a-Si:H/a-Si,Ge:H interface. The estimated trap concentration is around 10{sup 11}/cm{sup 2} and is independent of temperature and applied bias, ruling out the creation of the traps during the filling pulse. The authors also report results on samples in which a-Si:H/a-Si,Ge:H interface has been modified during growth to alter the concentration of the hole traps.

Although a-Si,Ge:H alloys have been increasingly studied in recent years because of their desired tunable band gaps for application in tandem solar cells, the relation between the mid gap defects with solar cell performance is still not completely clear. The authors have characterized the defect state structure in a series of device quality glow discharge produced a-Si,Ge:H alloys with Ge content ranging from 30 at.% to 50 at.% using capacitance profiling, modulated photocurrent, transient junction photocurrent and photocapacitance measurements. As previously reported, these methods allows one to identify two types of thermally induced defect transitions plus two types of optical transitions from deep defects. In the current study the authors have examined the changes in these defects, along with the changes in the hole mobility-time products, that result from prolonged light exposure. By comparing these changes in the annealed state and light soaked state of the same sample, they attempt to correlate the changes in defects with the hole mobility-time product. In general, although all of the defect bands are found to increase after light soaking, the relative factor is found to be different for the various defect transitions within the same sample. The authors also try to identify amore » defect bands may be acting as a safe electron trap, enhancing the lifetime of the minority carriers. They propose that the observed decrease of this defect band relative to the midgap defect band with light soaking could be a significant factor in determining the degradation of these a-Si,Ge:H alloys in the device performance.« less

We have carried out a detailed study of the energy distribution of deep defects for high quality glow discharge a-Si,Ge:H alloys using both thermal emission and optical Methods: drive-level capacitance profiling, transient photocapacitance and photocurrent plus modulation photocurrent spectroscopy. Four distinct bands of transitions involving defect states have been identified: two associated with thermal transitions, and the other two related to optical transitions. We have, for the first time, observed a negative signal in the photocapacitance spectra at photon energies near 1.2eV. This striking aspect verifies the presence of a distinct defect band above Ep from which electron thermal emission is greatly suppressed. Our Measurements also disclose a fairly narrow defect band below the Fermi level which contrasts with the defect properties observed in a-Si:H. Time resolved photocapacitance spectra indicate that this defect band exhibits configuration relaxation.

Bandtail defect carrier trapping dynamics in high quality photo-CVD grown a-Si1-xGex:H (x=0.3 and 0.62) and PECVD deposited a-Si:H films were studied using photo-modulated electron spin resonance (PMESR). Comparison of the dark spin densities with junction capacitance (drive-level profiling) methods indicate that a majority of the defects are neutral in the a-Si:H and 30% Ge samples, but the majority of the defects in the 62% Ge sample are charged. Lineshape deconvolution of the PMESR signals in the in-phase and quadrature phase as a function of photo-modulation frequency, excitation energy and excitation intensity for both intrinsic (state A) and light soaked (state B) states revealed three significant insights: in state A all samples behave similarly, state B behavior of the a-Si:H is dramatically different from the state B alloyed samples, and strong evidence for 'safe hole traps' (SHT) is observed in the state B a-Si:H material.

The effect of C impurities in a-Si:H in levels of 0.4 to 2.6 at. % were studied over a wide range of metastable defect densities. Three complimentary experimental techniques [electron spin resonance (ESR), drive-level capacitance (DLC) and photo-current] were employed to track the material's defect density with light soaking and annealing, as well as Urbach energies, midgap absorption and mobility gaps energies as a function of the C content. Our results show C impurities have a definite effect on the initial and saturated defect densities, as well as the midgap absorption and Urbach energies at levels 1 at. % and above. The results indicate that C acts mainly as a center for increased disorder in the material which results in an increase in the bandtail widths, and consequently an increase in intrinsic defects. Comparison to the ESR and drive-level data show an excellent agreement between these two techniques in determining the bulk defect densities in a-Si:H.

This report describes works to use transient photocapacitance and photocurrent measurements to determine the deep defect distribution and processes in low-band-gap a-Si,Ge:H alloys. Samples for these studies were produced by the photochemical vapor deposition (photo-CVD) growth method and were obtained through a collaboration with researchers at the University of Delaware. This report discusses how a detailed comparison between the photocapacitance and photocurrent spectra can be used to separately examine the majority and minority carrier processes. The results are as follows: (1) The midgap defect densities in the alloy regime near 1.3 eV can be as low as 5 {times} 10{sup 16} cm{sup {minus}3} in such photo-CVD samples. (2) There exists a second defect band roughly 0.4 eV below E{sub c} of a similar magnitude to the midgap defect density that exhibits significant lattice relaxation behavior in its electron trapping dynamics. (3) The hole {mu}{tau} products determined for the lowest defect sample are roughly 5 {times} 10{sup {minus}10} cm{sup 2}/V, comparable with the highest hole {mu}{tau} products reported in sandwich geometry measurements for alloys in this composition range. (4) The hole {mu}{tau} is found to be roughly inversely proportional to the midgap defect density for the samples studied. This is consistentmore » with the fact that the effective minority carrier lifetime for such measurements is limited by the deep state trapping time.« less

The work performed for this contract continued investigations of the origins of metastable effectS in a-Si:H through three kinds of studies: (1) the effect of carbon impurities in a-Si:H samples at low concentrations using drive-level capacitance profiling measurements on samples whose carbon content was intentionally modulated spatially during growth, (2) the characterization of metastable states in n-type doped a Si:H samples caused by quench cooling and by light-soaking with partial annealing, and (3) the use of depletion-width-modulated ESR spectroscopy together with junction capacitance spectroscopy to investigate deep defect states for various metastable states of a 10- and an 80-Vppm PH{sub 3}-doped a-Si:H sample.

Depletion-width-modulated (DWM) ESR spectroscopy and junction capacitance techniques were employed to investigate deep-defect states in various metastable states of 10 and 80 Vppm PH3-doped a-Si:H. From the joint application of these methods, we enumerate the change in total spin and charge associated with emission of carriers from states within the mobility gap resulting from a modulated bias voltage. We conclude that the magnitude of the modulated spin-to-charge ratio is nearly unity, consistent with earlier similar investigations of n-type a-Si:H, where the D-/D0 transition was shown to dominate. Furthermore, we present results of a previously unreported “quadrature” DWM-ESR signal of large magnitude under a wide range of experimental conditions. Similar related effects are also reported from spin- and capacitance-transient studies. These results clearly demonstrate that the changes in spin significandy lag corresponding changes in charge.

Capacitance vs. temperature, deep-level transient spectroscopy (DLTS), and transient photocapacitance spectroscopy have been used to investigate the amorphous-crystalline silicon interface region of a device made of hydrogenated amorphous silicon deposited on a lightly doped n-type crystalline silicon.By comparing our results between substrates with and without oxide contamination with those in a earlier study, we have been able to correlate the effects of substrate preparation on the density of interface states.

Recent results obtained by applying two methods, drive-level capacitance profiling and transient photocapacitance spectroscopy, to the study of deep defects in undoped hydrogenated amorphous silicon (a-Si:H) are reviewed. From the first method, we illustrate how it is possible to obtain the density, energy distribution, electronic occupation and spatial distribution of light-induced metastable deep defects for a set of hydrogenated amorphous silicon samples with well-characterized impurity levels. These results strongly suggest an extrinsic carbon-related component to the degree of instability in some films. We also illustrate how a detailed comparison between transient photocapacitance and photocurrent spectra provides specific information about gap state dynamics and carrier-transport processes in a-Si:H films and, in particular, metastable changes in those properties.

From junction-capacitance measurements we have determined the density, energy distribution, and electronic occupation of light-induced metastable defects near the midgap for a set of nearly intrinsic hydrogenated-amorphous-silicon samples with well-characterized impurity levels. In particular, we have inferred the changes in both neutral and negative dangling bonds for a series of isochronal anneals between the light-soaked state and full-dark-annealed state of each sample. Our results indicate that the dominant defect-creation mechanism is not Si--Si bond breaking, and also indicate the existence of at least two quasi-independent metastable defect-creation processes.

We have observed a reversible photoinduced modification of the bulk density of gap states in a‐Si:H associated with the Staebler–Wronski effect. A detailed numerical analysis of diode admittance and deep level transient spectroscopy measurements shows that the changes in these properties after illumination can be explained by a lowering of the bulk Fermi level and an increase in the density of states below midgap.

We have developed a new method of capacitance profiling which is greatly superior to standard profiling techniques for materials like amorphous silicon that contain high densities of deep gap states. This technique, which makes use of the variation of the junction capacitance with the alternating voltage amplitude, is largely immune to the effects of surface states and is readily interpreted in terms of a simple integral over the density of states, g(E). This method is applicable to both doped and semi‐insulating undoped samples.

We have carried out a detailed study of the competition between optical and thermal transitions from mobility gap states in hydrogenated amorphous silicon films. By employing transient photocapacitance and capacitance DLTS techniques on n-type doped films, we have observed the dangling bond optical transitions:D− → D0 + e and D0 → D+ + e, and the thermal transitions: D− → D0 + e and D0 → D0 + h. From the transition energies we have determined that the degree of lattice relaxation for dangling bonds does not exceed 0.1 eV and that the value Ueff of the D−/D0 splitting is 0.3 ± 0.1 eV. Voltage pulse photocapacitance studies on undoped films revealed the existence of the optical transition D−/D0 + e. In addition, in all films we have observed a photocapacitance signal due to optical transitions from the valence band tail states (over the energy range 1.4 to 1.9 eV) at temperatures as high as 440 K, in spite of the expectation that such shallow photoexcited holes would immediately be thermally emitted yielding no photocapacitance signal. We discuss possible explanations for this result by considering two different trapping models.

A novel a-Si:H/c-Si Schottky diode heterostructure device premits the study of the capacitive response to relatively low temperatures (25 K) and also allows fast pulse filling capture measurements of electrons from the c-Si substrate into a-Si:H defect states. These latter measurements, as well as capacitance vs. temperature measurements on these diodes, indicate a nearly zero conduction band offset (50±50 meV). We also have observed trapping of holes at the a-Si:H/c-Si valence band discontinuity ΔEv. A clear threshold for the subsequent optical release of these trapped holes by sub-bandgap light yields a value of ΔEv = 0.58±0.02 eV. Finally, photocapacitance spectra along with thermally stimulated capacitance (TSCAP) measurements indicate an anomalously large (l×1018/cm3) Gaussian-shaped defect band located a Ec - 0.88 eV with a FWHM of 0.46 eV. Model calculations of the high temperature capacitance-voltage dependence indicate these defects lie predominately within 350 Å of the a-Si:H/c-Si interface.

The effects of light saturation on the properties of undoped a-Si:H films were studied by a new capacitance profiling technique which can be used to directly determine changes in the dangling bond density of states near midgap. Coplanar conductivity and capacitance vs. temperature measurements save the changes in activation energies for electrical conductivity. These studies indicate that, while substantial increases in the dangling bond densities are observed for most samples, the detailed behavior of the light induced changes in these films are inconsistent with the creation of such defects by breaking weak valence band tail states.

Amorphous-crystalline heterostructures composed of sub-micron thick undoped amorphous hydrogenated silicon deposited on lightly doped n-type crystalline silicon substrates have been studied by capacitance techniques. Capacitance vs. temperature scans along with model calculations on these samples are used to investigate the amorphous-crystalline silicon interface region. We deduce the existence of an anomalously defective a-Si:H region extending roughly 1000 Angstroms from the growth interface. We also deduce considerable fluctuations in the interface potential which indicate lateral variations of ±20% in the defect distritribution over a 1000 Angstrom scale.

We have studied the light induced instability problem in hydrogenated amorphous silicon using junction capacitance techniques. These techniques are used to examine specific changes in the density of gap states, and occupation of gap states, for undoped a-Si:H samples after light saturation and for a series of partial anneal “states” which culminate in the original dark annealed state (state A). We find that the observed changes in the metastable occupied and unoccupied defects contradict the Si-Si bond breaking model and indicate at least two defect creation processes. In several samples we also find clear evidence that the metastable defect distribution near midgap has a slightly different energy distribution than the stable deep state (dangling bond) distribution. At the same time, these results seem to be qualitatively consistent with many aspects of recent ESR and optical absorption studies of metastable defect creation. We discuss these findings in terms of alternative possible microscopic models for metastable effects in a-Si:H.

The density of gap states in the bulk of intrinsic a-SiH has been probed using depletion width modulation electron spin resonance spectroscopy (DWM ESR) as well as complementary capacitance techniques. Our sample consists of a 2.85 micron thick layer of undoped a-Si:H sandwiched between a large area Pd Schottky barrier contact and a p+ c-Si substrate, allowing charge-counting capacitance and spin-counting ESR measurements to be performed on the same sample. DWM ESR measures the spin change that occurs when electrons are removed from gap states by increasing reverse bias on a Schottky barrier. The phase of the signal indicates whether unpaired spins are created or destroyed with increasing bias, thus revealing the defect charge state at the Fermi level The DWM ESR signal from our sample indicates that removing electrons from gap states leads to a reduction of the spin signal. This is qualitatively consistent with a band of Do states near EFo. However, for all metastable states and at all temperatures studied, the magnitude of the DWM ESR signal account for only about 14% of the responding charge as determined by junction capacitance. This would occur only if the majority of the filled bulk gap states were doubly occupied with a small correlation energy Ueff. In that case the majority of transitions caused by depletion width modulation would be D−/D+ which would produce no spin change. Model calculations show that the small observed Do/D+ DWM ESR signal would indeed result from the occupation statistics for a near zero value of Ueff at the moderate temperatures of the experiment. Comparison with our data sets the overall limits If −20meV < Ueff < 50 meV. Implication for recent models of the density of states in intrinsic a-Si:H are discussed.

A large number of different measurements which are sensitive to gap states in hydrogenated amorphous silicon have been analyzed over the past few years in an attempt to determine the generic form of the density of states function within the mobility gap of this material. These results tend to support one or the other of two quite different functions: a) the field-effect density of states, or b) the DLTS density of states. In this paper we review the evidence for the density of states function determined for a-Si:H by deep-level transient spectroscopy (DLTS). We argue that the strong and growing support for the DLTS picture is evidence that the two general forms for the density of states relate to different spatial regions of the specimen, e.g. interface vs. bulk properties.

This report contains results of Phase II of research to investigate metastable defect creation processes in hydrogenated amorphous silicon. The study relied primarily on junction capacitance methods to monitor the changes in deep defect distribution. Results obtained applying capacitance profiling methods to the study of undoped samples are summarized and indicate a significant role of extrinsic impurities in the degree of light-induced degradation that occurred. Photocapacitance transient measurements were taken to investigate changes in undoped a-Si:H. Studies were also begun of metastable changes in n-type doped a-Si:H samples by using both the drive-level capacitance profiling technique and transient photocapacitance methods, and results are described. 22 refs., 10 figs., 1 tab.