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Chemical beam epitaxy for high efficiency photovoltaic devices

InP-based multijunction tandem solar cells show great promise for the conversion efficiency (eta) and high radiation resistance. InP and its related ternary and quanternary compound semiconductors such as InGaAs and InGaAsP offer desirable combinations for energy bandgap values which are very suitable for multijunction tandem solar cell applications. The monolithically integrated InP/In(0.53)Ga(0.47)As tandem solar cells are expected to reach efficiencies above 30 percent. Wanlass, et.al., have reported AMO efficiencies as high as 20.1% for two terminal cells fabricated using atmospheric-pressure metalorganic vapor phase epitaxy (APMOVPE). The main limitations in their technique are first related to the degradation of the intercell ohmic contact (IOC), in this case the In(0.53)Ga(0.47)As tunnel junction during the growth of the top InP subcell structure, and second to the current matching, often limited by the In(0.53)Ga(0.47)As bottom subcell. Chemical beam epitaxy (CBE) has been shown to allow the growth of high quality materials with reproducible complex compositional and doping profiles. The main advantage of CBE compared to metalorganic chemical vapor deposition (MOCVD), the most popular technique for InP-based photovoltaic device fabrication, is the ability to grow high purity epilayers at much lower temperatures (450 C - 530 C). In a recent report it was shown that cost-wise CBE is a breakthrough technology for photovoltaic (PV) solar energy progress in the energy conversion efficiency of InP-based solar cells fabricated using chemical beam epitaxy. This communication summarizes our recent results on PV devices and demonstrates the strength of this new technology.

Bensaoula, A.↗

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3 and MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductors materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating should work well for all III-V compound-based solar cells.

Moulot, Jacques↗

Naval Research Laboratory's programs in advanced indium phosphide solar cell development

The Naval Research Laboratory (NRL) has been involved in the development of solar cells for space applications since the 1960s. It quickly became apparent in this work that radiation damage caused to solar cells by electrons and protons trapped by the earth's magnetic field would seriously degrade the power output of photovoltaic arrays in extended missions. Techniques were therefore developed to harden the cells by shielding them with coverglass, etc. Ultimately, however, there is a limit to such approaches, which is determined by the radiation response of the semiconductor material employed. A desire for high efficiency and radiation resistance led to the development of alternative cell technologies such as GaAs, which has since become the technology of choice for many applications. InP cells are currently the most radiation resistant, high efficiency, planar cells known. NRL first sponsored InP solar cell technology in 1986, when Arizona State University was contracted to grow p/n cells by liquid phase epitaxy. NRL's interest in InP cells was generated by the results presented by Yamaguchi and his co-workers in the early 1980s on the remarkable radiation resistance of cells grown by diffusion of S into Zn doped p-type InP substrates. These cells also had beginning of life (BOL) efficiencies approximately 16%(AM0). Related to the radiation resistance of the cells was the fact that radiation-induced damage could be optically annealed by sunlight. Relatively large quantities of 1 x 2 cm(exp 2) diffused junction cells were made and were used on the MUSES-A and the EXOS-D satellites. These cells were also available in the U.S. through NIMCO, and were studied at NRL and elsewhere. Workers at NASA Lewis became involved in research in InP cells about the same time as NRL.

Summers, Geoffrey P.↗

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Moulot, Jacques↗

Understanding Cirrus Ice Crystal Number Variability for Different Heterogeneous Ice Nucleation Spectra

Along with minimizing parameter uncertainty, understanding the cause of temporal and spatial variability of the nucleated ice crystal number, Ni, is key to improving the representation of cirrus clouds in climate models. To this end, sensitivities of Ni to input variables like aerosol number and diameter provide valuable information about nucleation regime and efficiency for a given model formulation. Here we use the adjoint model of the adjoint of a cirrus formation parameterization (Barahona and Nenes, 2009b) to understand Ni variability for various ice-nucleating particle (INP) spectra. Inputs are generated with the Community Atmosphere Model version 5, and simulations are done with a theoretically derived spectrum, an empirical lab-based spectrum and two field-based empirical spectra that differ in the nucleation threshold for black carbon particles and in the active site density for dust. The magnitude and sign of Ni sensitivity to insoluble aerosol number can be directly linked to nucleation regime and efficiency of various INP. The lab-based spectrum calculates much higher INP efficiencies than field-based ones, which reveals a disparity in aerosol surface properties. Ni sensitivity to temperature tends to be low, due to the compensating effects of temperature on INP spectrum parameters; this low temperature sensitivity regime has been experimentally reported before but never deconstructed as done here.

Cirrus↗

62°S Witnesses the Transition of Boundary Layer Marine Aerosol Pattern Over the Southern Ocean (50°S–68°S, 63°E– 150°E) During the Spring and Summer: Results From MARCUS (I)

The Atmospheric Radiation Measurement Mobile Facility-2 was installed onboard the research vessel Aurora Australis to measure aerosol properties during the 2017-2018 Measurement of Aerosols, Radiation, and CloUds over the pristine Southern ocean (MARCUS) Experiment, providing unique data on aerosols latitudinal and seasonal variation, including south of 60 degrees S where previous observations are scarce. Data from a Cloud Condensation Nuclei (CCN) counter and Ultra-High-Sensitivity Aerosol Spectrometer show that both the number concentration (N-CCN) and size distribution of CCN-active aerosols, with diameters (D) between 60 nm < D < 1,000 nm are different over the North Southern Ocean (NSO) (50 degrees S-60 degrees S) and the South Southern Ocean (SSO) (62 degrees S-68 degrees S). The average NSO N-CCN at 0.2% and 0.5% supersaturation were 28% and 49% less than that over the SSO. This increase of CCN over the SSO is caused by the increase of aerosols with 60 nm < D < 200 nm, consistent with calculations of Aerosol Scattering Angstrom Exponents derived from a nephelometer. Aerosol hygroscopicity growth factor measured by the Hygroscopic Tandem Differential Mobility Analyzer stayed close to 1.41 for aerosols with 50 nm < D < 250 nm over the SSO, but increased from 1.30 to 1.67 over the NSO, indicating different chemical compositions. Both CCN and Ice Nucleating Particles (INPs) showed a stronger variation with season than with latitude. The variation of heat-labile and presumably proteinacous INPs suggests an increase of ice nucleating-active microbes in summer.

Niu, Qing↗

On the Role of Airborne Ice Nucleating Particles in Primary and Secondary Ice Formation Processes in Convective Midlatitude Clouds

Abstract Formation of ice in mixed-phase clouds may proceed via primary nucleation and secondary ice production (SIP). Primary nucleation involves the presence of ice nucleating particles (INPs), while SIP follows primary nucleation, resulting in ice crystal number concentrations N ice exceeding the number of INPs. The ice formation pathways in young congestus clouds are not well understood nor are the environmental conditions favorable for the onset of SIP. Coincident airborne measurements of INPs and N ice collected during the Secondary Production of Ice in Cumulus Experiment (SPICULE) campaign over the U.S. central Great Plains are reported for young congestus clouds. Number concentrations of INPs and N ice at temperatures between −10° and −20°C were used to categorize whether SIP was active in each analyzed cloud pass. Observational data suggested that fragmentation of freezing droplets (FFDs) was occurring and the most likely SIP mechanism for ice enhancement during the early stages of the sampled clouds, where higher cloud-base temperatures and stronger updrafts produced conditions favorable for the onset of FFD. Simple model simulations of a congestus cloud were used to compare predictions of N ice from newly implemented SIP mechanisms (including FFD) alongside those from the existing Hallett–Mossop (HM) mechanism. Although predicted N ice , when all SIP mechanisms were active, was in good agreement with observations, the dominant SIP mechanism in the model was predicted to be HM. The rate of heterogeneous freezing in raindrops was likely inhibiting realistic FFD rates in the simulated cloud. These discrepancies between the observations and simulations underscore the need for extended laboratory studies to formulate improved model representations of SIP in convective clouds.

Patnaude, Ryan J. [Department of Atmospheric Scien↗

Application of aerosol-ice nucleating particle closure to establish the leading parameters governing ice crystal number concentration under commonly observed mixed-phase cloud conditions

This is the final technical report for DOE DE-SC0021034 award entitled “Application of aerosol-ice nucleating particle closure to establish the leading parameters governing ice crystal number concentration under commonly observed mixed-phase cloud conditions”. The overarching objective of this project was to gain a predictive understanding of the processes that lead from aerosols to ice-nucleating particles (INPs) to ice crystal number concentrations (ICNCs) in stratiform mixed-phase clouds where supercooled water droplets and ice crystals coexist, and to inform climate model parameterizations. During this four-year project we addressed the three main research goals of this objective: 1) Study the aerosol-INP link; 2) Develop an aerosol-cloud column model (AC-1D); and 3) Study the INP-ICNC link. Those activities significantly advanced our predictive understanding of how to represent INPs in could models and its implications on ice crystal number concentrations. The results have been published in five peer-reviewed publications with three more in review and preparation. It allowed for collaboration resulting in additional fourteen peer-reviewed publications that are concerned with the objective of this research project. This research has been communicated to the scientific community at national and international meetings and conferences by numerous talks, seminars, and posters including fifteen invited presentations. This project allowed training of four graduate students and one postdoctoral research associate resulting in one M.S. thesis and advancement to Ph.D. candidacy.

54 ENVIRONMENTAL SCIENCES↗

The impact of aerosol mixing state on immersion freezing: insights from classical nucleation theory and particle-resolved simulations

Immersion freezing, initiated by ice-nucleating particles (INPs) in supercooled aqueous droplets, plays an important role in the formation of ice crystals within clouds. The efficiency of immersion freezing depends strongly on INP composition and, crucially, on the mixing state – how chemical species are distributed across the particle population. Here, we quantify the impact of aerosol mixing state on immersion freezing using a combined theoretical and particle-resolved modeling approach. We derive analytical expressions for the frozen fraction of internally and externally mixed INP populations based on classical nucleation theory, showing that the frozen fraction is sensitive to whether ice-active species are present in all particles or only in a subset of the population. We introduce a multi-species immersion freezing scheme into the particle-resolved model PartMC, using the water activity-based immersion freezing model (ABIFM) to compute freezing probabilities for mixed-composition particles. To improve computational efficiency, we implement a Binned Tau-Leaping algorithm and demonstrate an order-of-magnitude speedup with minimal accuracy loss. Simulations reproduce the analytical trends in limiting cases and extend the analysis to more general aerosol populations, where mixing state continues to exert a substantial control on frozen fraction. Sensitivity analyses across particle size, species type, and cooling condition reveal that the mixing state effect is most pronounced when small amounts of highly efficient INPs are mixed with less efficient materials. These findings underscore the need to represent aerosol mixing state explicitly in models of heterogeneous ice nucleation to reduce uncertainty in cloud-phase partitioning.

54 ENVIRONMENTAL SCIENCES↗

Material growth and characterization for solid state devices

Manganese was used as the dopant for p-type InGaAs layers grown on semi-insulating (Fe-doped) and n-type (Sn-doped) InP substrates. Optical, electrical (Hall) and SIMS measurements were used to characterize the layers. Mn-diffusion into the substrate (during the growth of In GaAs) was observed only when Fe-doped substrates were used. Quaternary layers of two compositions corresponding to wavelengths (energy gaps) of approximated 1.52 micrometers were successfully grown at a constant temperature of 640 C and InP was grown in the temperature range of 640 C to 655 C. A study of the effect of pulses on the growth velocity of InP indicated no significant change as long as the average applied current was kept constant. A system for depositing films of Al2O3 by the pyrolysis of aluminum isopropoxide was designed and built. Deposited layers on Si were characterized with an ellipsometer and exhibited indices of refraction between 1.582 and 1.622 for films on the order of 3000 A thick. Undoped and p-type (Mn-doped) InGaAs epitaxial layers were also grown on Fe-doped InP substrates through windows in sputtered SiO2 (3200 A thick) layers.

Stefanakos, E. K.↗

Brazil's remote sensing activities in the Eighties

Most of the remote sensing activities in Brazil have been conducted by the Institute for Space Research (INPE). This report describes briefly INPE's activities in remote sensing in the last years. INPE has been engaged in research (e.g., radiance studies), development (e.g., CCD-scanners, image processing devices) and applications (e.g., crop survey, land use, mineral resources, etc.) of remote sensing. INPE is also responsible for the operation (data reception and processing) of the LANDSATs and meteorological satellites. Data acquisition activities include the development of CCD-Camera to be deployed on board the space shuttle and the construction of a remote sensing satellite.

Raupp, M. A.↗

Radiation and temperature effects in gallium arsenide, indium phosphide and silicon solar cells

The effects of radiation on performance are determined for both n(+)p and p(+)n GaAs and InP cells and for silicon n(+)p cells. It is found that the radiation resistance of InP is greater than that of both GaAs and Si under 1 MeV electron irradiation. For silicon, the observed decreased radiation resistance with decreased resistivity is attributed to the presence of a radiation induced boron-oxygen defect. Comparison of radiation damage in both p(+)n and n(+)p GaAs cells yields a decreased radiation resistance for the n(+)p cell attributable to increased series resistance, decreased shunt resistance, and relatively greater losses in the cell's p-region. For InP, the n(+)p configuration is found to have greater radiation resistance than the p(+)n cell. The increased loss in this latter cell is attributed to losses in the cell's emitter region. Temperature dependency results are interpreted using a theoretical relation for dVoc/cT which predicts that increased Voc should results in decreased numerical values for dPm/dT. The predicted correlation is observed for GaAs but not for InP a result which is attributed to variations in cell processing.

Weinberg, I.↗

Rapid thermal annealing of indium phosphide compound semiconductors

The rapid thermal annealing (RTA) of indium phosphide (InP) substrates using a proximity contact method and silicon nitride encapsulation is investigated. The surface conditions of the InP substrates following cleaning with procedures A and B are analyzed. Procedure A involves using an iodic acid solution to remove work-damage InP surface layers and B is a degasssing process and hydrofluoric acid solution for native oxide removal. AES, XPS, and SIMS data of the proximity contact and silicon nitride encapsulated annealed samples are examined. The data reveal that RTA using proximity contact with silicon wafers does not provide adequate protection; however, the InP sample is successfully annealed when protected by a silicon nitride encapsulant.

Biedenbender, Michael D.↗

Radiation and temperature effects in gallium arsenide, indium phosphide, and silicon solar cells

The effects of radiation on performance are determined for both n+p and p+n GaAs and InP cells and for silicon n+p cells. It is found that the radiation resistance of InP is greater than that of both GaAs and Si under 1-MeV electron irradiation. For silicon, the observed decreased radiation resistance with decreased resistivity is attributed to the presence of a radiation-induced boron-oxygen defect. Comparison of radiation damage in both p+n and n+p GaAs cells yields a decreased radiation resistance for the n+p cell attributable to increased series resistance, decreased shunt resistance, and relatively greater losses in the cell's p-region. For InP, the n+p configuration is found to have greater radiation resistance than the p+n cell. The increased loss in this latter cell is attributed to losses in the cell's emitter region. Temperature dependency results are interpreted using a theoretical relation for dVoc/dT, which predicts that increased Voc should result in decreased numerical values for dPm/dT. The predicted correlation is observed for GaAs but not for InP, a result which is attributed to variations in cell processing.

Weinberg, I.↗

Progress in indium phosphide solar cell research

Progress, dating from the start of the Lewis program, is reviewed emphasizing processing techniques which have achieved the highest efficiencies in a given year. To date, the most significant achievement has been attainment of AM0 total area efficiencies approaching 19 percent. Although closed tube diffusion is not considered to be an optimum process, reasonably efficient 2cm x 2cm and 1cm x 2cm InP cells have been produced in quantity by this method with a satellite to be launched in 1990 using these cells. Proton irradiation of these relatively large area cells indicates radiation resistance comparable to that previously reported for smaller InP cells. A similar result is found for the initial proton irradiations of ITO/InP cells processed by D. C. sputtering. With respect to computer modelling, a comparison of n/p homojunction InP and GaAs cells of identical geometries and dopant concentrations has confirmed the superior radiation resistance of InP cells under 1 MeV electron irradiations.

Weinberg, Irving↗

InP/Ga0.47In0.53As monolithic, two-junction, three-terminal tandem solar cells

The work presented has focussed on increasing the efficiency of InP-based solar cells through the development of a high-performance InP/Ga(0.47)In(0.53)As two-junction, three-terminal monolithic tandem cell. Such a tandem is particularly suited to space applications where a radiation-hard top cell (i.e., InP) is required. Furthermore, the InP/Ga(0.47)In(0.53)As materials system is lattice matched and offers a top cell/bottom cell bandgap differential (0.60 eV at 300 K) suitable for high tandem cell efficiencies under AMO illumination. A three-terminal configuration was chosen since it allows for independent power collection from each subcell in the monolithic stack, thus minimizing the adverse impact of radiation damage on the overall tandem efficiency. Realistic computer modeling calculations predict an efficiency boost of 7 to 11 percent from the Ga(0.47)In(0.53)As bottom cell under AMO illumination (25 C) for concentration ratios in the 1 to 1000 range. Thus, practical AMO efficiencies of 25 to 32 percent appear possible with the InP/Ga(0.47)In(0.53)As tandem cell. Prototype n/p/n InP/Ga(0.47)In(0.53)As monolithic tandem cells were fabricated and tested successfully. Using an aperture to define the illuminated areas, efficiency measurements performed on a non-optimized device under standard global illumination conditions (25 C) with no antireflection coating (ARC) give 12.2 percent for the InP top cell and 3.2 percent for the Ga(0.47)In(0.53)As bottom cell, yielding an overall tandem efficiency of 15.4 percent. With an ARC, the tandem efficiency could reach approximately 22 percent global and approximately 20 percent AMO. Additional details regarding the performance of individual InP and Ga(0.47)In(0.53)As component cells, fabrication and operation of complete tandem cells and methods for improving the tandem cell performance, are also discussed.

Wanlaas, M. W.↗

In(X)Ga(1-X) As Strain-Layer Multiple-Quantum-Well Laser Diodes

Fabricated on InP substrates, devices operate at room temperature, emitting at wavelengths near 1.8 micrometers. By suitable modification of structure of devices, possible to achieve operation at any wavelength from 1.6 to 2.5 micrometers: this range important in lidar and in remote sensing of atmospheric gases. Quantum-well and barrier layers sandwiched between two 60-nm-thick layers of lattice-matched InGaAs. InGaAs layers sandwiched between two 150-nm-thick layers of InGaAsP. Those layers sandwiched, in turn, between InP substrate and InP cladding layer. Also layer of InGaAs atop InP cladding layers.

Forouhar, Siamak↗

Effects of plasma hydrogenation on trapping properties of dislocations in heteroepitaxial InP/GaAs

In previous work, we have demonstrated the effectiveness of a post-growth hydrogen plasma treatment for passivating the electrical activity of dislocations in metalorganic chemical vapor deposition (MOCVD) grown InP on GaAs substrates by a more than two order of magnitude reduction in deep level concentration and an improvement in reverse bias leakage current by a factor of approximately 20. These results make plasma hydrogenation an extremely promising technique for achieving high efficiency large area and light weight heteroepitaxial InP solar cells for space applications. In this work we investigate the carrier trapping process by dislocations in heteroepitaxial InP/GaAs and the role of hydrogen passivation on this process. It is shown that the charge trapping kinetics of dislocations after hydrogen passivation are significantly altered, approaching point defect-like behavior consistent with a transformation from a high concentration of dislocation-related defect bands within the InP bandgap to a low concentration of individual dislocation related deep levels, before and after passivation. It is further shown that the 'apparent' activation energies of dislocation related deep levels, before and after passivation, reduce by approximately 70 meV as DLTS fill pulse times are increased from 1 microsecond to 1 millisecond. A model is proposed which explains these effects based on a reduction of Coulombic interaction between individual core sites along the dislocation cores by hydrogen incorporation. Knowledge of the trapping properties in these specific structures is important to develop optimum, low loss heteroepitaxial InP cells.

Ringel, S. A.↗