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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Pure-Water-Fed Forward-Bias Bipolar Membrane CO 2 Electrolyzer

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchangelayer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm –2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h –1 decay rates at 150 and 300 mA cm –2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer– electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. Furthermore, all these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enabling Stable and Salt-Free Formic Acid Production via Reactive Interface Optimization in Forward-Bias Bipolar-Membrane CO2 Electrolyzers

Electrochemical conversion of CO2 to liquid products is limited by parasitic reactions that consume products and destabilize operation. Here, we show that salt-free formic acid synthesis in a forward-bias bipolar-membrane CO2 electrolyzer is governed by a coupled reaction-transport instability driven by parasitic anode formic acid oxidation. Operando mass spectrometry reveals that this process proceeds through CO-mediated poisoning, identifying catalyst tolerance to CO as a key descriptor of anode selectivity. Among the catalysts examined, PtRu/C preferentially promotes hydrogen oxidation over formic acid oxidation. Coupling this catalyst with transport-interface engineering improves product removal, enhances Faradaic and energy efficiency, and enables stable operation at 200 mA/cm2 for 190 h with a voltage decay of 0.64 mV/h. Techno-economic analysis indicates an 18% reduction in minimum selling price and highlights product concentration as the dominant cost lever. These results establish a general framework for suppressing product oxidation in liquid-product electrolyzers.

Hu, Leiming↗

Forward-bias tunneling - A limitation to bipolar device scaling

Forward-bias tunneling is observed in heavily doped p-n junctions of bipolar transistors. A simple phenomenological model suitable to incorporation in device codes is developed. The model identifies as key parameters the space-charge-region (SCR) thickness at zero bias and the reduced doping level at its edges which can both be obtained from CV characteristics. This tunneling mechanism may limit the maximum gain achievable from scaled bipolar devices.

Del Alamo, Jesus A.↗

Forward-bias capacitance and current measurements for determining lifetimes and band narrowing in p-n junction solar cells

A new method is described and illustrated for determining the minority-carrier diffusion length and lifetime in the base region of p-n junction solar cells. The method requires only capacitance measurements at the device terminals and its accuracy is estimated to be + or - 5%. It is applied to a set of silicon p-n junction devices and the values of the diffusion lengths agree with those obtained using the current response to X-ray excitation but disagree with those obtained by the OCVD method. The reasons for the relative inaccuracy of OCVD applied to silicon devices are discussed. The capacitance method includes corrections for a two-dimensional fringing effects which occur in small area devices. For a device having highly-doped base region and surface (emitter) layer, the method can be extended to enable the determination of material properties of the degenerately doped surface layer. These material properties include the phenomenological emitter lifetime and a measure of the energy band-gap narrowing in the emitter. An alternate method for determining the energy band-gap narrowing from temperature dependence of emitter current is discussed and demonstrated.

Neugroschel, A.↗

Transport of majority and minority carriers in 2-micron-diameter Pt-GaAs Schottky barriers

An experimental study of small area (2-micron diameter) Pt-GaAs Schottky barrier diodes has been made, by using a wafer chip with a matrix of these diodes lying within approximately a minority carrier diffusion length of one another. Using one diode as collector and another as emitter, transistor measurements indicated that the dominant contribution to the current is the majority-carrier thermionic field emission current for large forward-bias voltage of the emitter junction (V-EB no less than about 0.4 V), whereas the smaller forward-bias (V-EB no greater than about 0.4 V) recombination in the space-charge region was most important. The minority carrier injection ratio is measurable only for large forward-bias voltages, decreasing from about 0.02 to 0.00001 as VEB increases from 0.5 to 1.0 V. The minority carrier diffusion length was measured to be about 1.3 microns. These results are of considerable significance for the understanding and optimization of the performance of these devices as classical detectors and mixers.

Chan, E. Y.↗

Exploring transport mechanisms in atomic precision advanced manufacturing enabled pn junctions

We investigate the different transport mechanisms that can occur in pn junction devices made using atomic precision advanced manufacturing at temperatures ranging from cryogenic to room temperature. We first elucidate the potential cause of the anomalous behavior observed in the forward-bias response of these devices in recent cryogenic temperature measurements, which deviates from the theoretical response of a silicon Esaki diode. These anomalous behaviors include current suppression at low voltages in the forward-bias response and a much lower valley voltage at cryogenic temperatures than theoretically expected for a silicon diode. To investigate the potential causes of these anomalies, we studied the effects of a few possible transport mechanisms, including band-to-band tunneling, bandgap narrowing, potential impact of non-Ohmic contacts, band quantization, impact of leakage, and inelastic trap-assisted tunneling, through semi-classical simulations. We find that a combination of two sets of band-to-band tunneling (BTBT) parameters can qualitatively approximate the shape of the tunneling current at low bias. This can arise from band quantization and realignment due to the strong potential confinement in δ-layers. We also find that the lower-than-theoretically-expected valley voltage can be attributed to modifications in the electronic band structure within the δ-layer regions, leading to a significant bandgap narrowing induced by the high density of dopants. Finally, we extend our analyses to room temperature operation and predict that trap-assisted tunneling (TAT) facilitated by phonon interactions may become significant, leading to a complex superposition of BTBT and TAT transport mechanisms in the electrical measurements.

band gap↗

Thermally-restorable optical degradation and the mechanism of current transport in Cu2S-CdS photovoltaic cells

The photovoltaic properties of single-crystal Cu2S-CdS heterojunctions have been investigated as a function of heat treatment by detailed measurements of the dependence of short-circuit current on photon energy, temperature, and the state of optical degradation or enhancement. A coherent picture is formulated for the relationship between enhancement and optical degradation, and their effect on the transport of short-circuit photoexcited current and dark, forward-bias current in the cell. Optical degradation in the Cu2S-CdS cell is shown to be closely identical to optical degradation of lifetime in a homogeneous CdS:Cd:Cu crystal, indicating that the CdS:Cu layer near the junction interface controls carrier transport in the cell. It is proposed that both the photoexcited short-circuit current and the dark, forward-bias current are controlled by a tunneling-recombination process through interface states.

Fahrenbruch, A. L.↗

Diffusion length damage coefficient and annealing studies in proton-irradiated InP

We report on the measurement of the diffusion length damage coefficient (K(sub L)) and the annealing characteristics of the minority carrier diffusion length (L(sub n)) in Czochralski-grown zinc-doped indium phosphide (InP), with a carrier concentration of 1 x 10(exp l8) cm(exp -3). In measuring K(sub L) irradiations were made with 0.5 MeV protons with fluences ranging from 1 x 10(exp 11) to 3 x 10(exp 13) cm(exp -2). Pre- and post-irradiation electron-beam induced current (EBIC) measurements allowed for the extraction of L(sub n) from which K(sub L) was determined. In studying the annealing characteristics of L(sub n) irradiations were made with 2 MeV protons with fluence of 5 x 10(exp 13) cm(exp -2). Post-irradiation studies of L(sub n) with time at room temperature, and with minority carrier photoinjection and forward-bias injection were carried out. The results showed that recovery under Air Mass Zero (AMO) photoinjection was complete. L(sub n) was also found to recover under forward-bias injection, where recovery was found to depend on the value of the injection current. However, no recovery of L(sub n) after proton irradiation was observed with time at room temperature, in contrast to the behavior of 1 MeV electron-irradiated InP solar cells reported previously.

Hakimzadeh, Roshanak↗

Quantitative analysis of leakage current in III-nitride micro-light-emitting diodes

In this study, the electrical characteristics under forward- and reverse-bias conditions of III-nitride blue and green micro-light-emitting diodes (μLEDs) are analyzed. A fitting model is proposed to determine the contributions of reverse leakage current and the effectiveness of sidewall treatments. Moreover, the forward-bias currents of the μLEDs are examined using the extracted ideality factor to examine the impacts of sidewall defects. The results show that sidewall treatments are highly effective for suppression of leakage currents. From the efficiency perspective, higher wall-plug efficiency (WPE) than external quantum efficiency (EQE) is observed when the operating voltage is lower than the photon voltage in both blue and green 20 × 20 μm 2 devices. This enhancement of the WPE over the EQE is due to the suppression of Shockley–Read–Hall (SRH) nonradiative recombination. These observations indicate that μLEDs with sidewall treatments not only improve optical performance but also further enhance the electrical performance of devices by suppressing the leakage current paths due to SRH nonradiative recombination processes.

42 ENGINEERING↗

Heat treatment effects in Cu2S-CdS heterojunction photovoltaic cells

The dependence of the short-circuit current on photon energy, temperature, and the state of optical degradation (or enhancement) is determined in a study of the photovoltaic properties of Cu2S-CdS single-crystal heterojunctions. A coherent formulation is proposed for the relationship between enhancement and optical degradation and for their effects on the transport of a short-circuit photoexcited current and dark forward-bias current in a photovoltaic cell. Optical degradation in a Cu2S-CdS cell is shown to be identical to the optical degradation of lifetime in a homogeneous CdS:Cd:Cu crystal.

Fahrenbruch, A. L.↗

Development of an Accelerated Test Design for Predicting the Service Life of the Solar Array at Mead, Nebraska

An accelerated life test is described which was developed to predict the life of the 25 kW photovoltaic array installed near Mead, Nebraska. A quantitative model for accelerating testing using multiple environmental stresses was used to develop the test design. The model accounts for the effects of thermal stress by a relation of the Arrhenius form. This relation was then corrected for the effects of nonthermal environmental stresses, such as relative humidity, atmospheric pollutants, and ultraviolet radiation. The correction factors for the nonthermal stresses included temperature-dependent exponents to account for the effects of interactions between thermal and nonthermal stresses on the rate of degradation of power output. The test conditions, measurements, and data analyses for the accelerated tests are presented. Constant-temperature, cyclic-temperature, and UV types of tests are specified, incorporating selected levels of relative humidity and chemical contamination and an imposed forward-bias current and static electric field.

Gaines, G. B.↗

Forward- and reverse-bias tunneling effects in n/+/p silicon solar cells

Excess currents due to field-assisted tunneling in both forward and reverse bias directions have been observed in n(+)-p silicon solar cells. These currents arise from the effect of conducting paths produced in the depletion layer by n(+) diffusion and cell processing. Forward-bias data indicate a small potential barrier with height of 0.04 eV at the n(+) end of conducting paths. Under reverse bias, excess tunneling currents involve a potential barrier at the p end of the conducting paths, the longer paths being associated with smaller barrier heights and dominating at the lower temperatures. Low-reverse-bias data give energy levels of 0.11 eV for lower temperatures (253-293 K) and 0.35 eV for higher temperatures (293-380 K). A model is suggested to explain the results.

Garlick, G. F. J.↗

Tunneling effects in the current-voltage characteristics of high-efficiency GaAs solar cells

Evidence is that tunneling via states in the forbidden gap is the dominant source of excess current in the dark current-voltage (I-V) characteristics of high-efficiency DMCVD grown Al(x)Ga(1-x)As/GaAs(x is equal to or greater than 0.85) solar cells. The dark forward and reverse I-V measurements were made on several solar cells, for the first time, at temperatures between 193 and 301 K. Low-voltage reverse-bias I-V data of a number of cells give a thermal activation energy for excess current of 0.026 + or - 0.005 eV, which corresponds to the carbon impurity in GaAs. However, other energy levels between 0.02 eV and 0.04 eV were observed in some cells which may correspond to impurity levels introduced by Cu, Si, Ge, or Cd. The forward-bias excess current is mainly due to carrier tunneling between localized levels created in the space-charge layer by impurities such as carbon, which are incorporated during the solar cell growth process. A model is suggested to explain the results.

Kachare, R.↗

Measured and Simulated Dark J-V Characteristics of a-Si:H Single Junction p-i-n Solar Cells Irradiated with 40 keV Electrons

The effect of 40 keV electron irradiation on a-Si:H p-i-n single-junction solar cells was investigated using measured and simulated dark J-V characteristics. EPRI-AMPS and PC-1D simulators were explored for use in the studies. The EPRI-AMPS simulator was employed and simulator parameters selected to produce agreement with measured J-V characteristics. Three current mechanisms were evident in the measured dark J-V characteristics after electron irradiation, namely, injection, shunting and a term of the form CV(sup m). Using a single discrete defect state level at the center of the band gap, good agreement was achieved between measured and simulated J-V characteristics in the forward-bias voltage region where the dark current density was dominated by injection. The current mechanism of the form CV(sup m) was removed by annealing for two hours at 140 C. Subsequent irradiation restored the CV(sup m) current mechanism and it was removed by a second anneal. Some evidence of the CV(sup m) term is present in device simulations with a higher level of discrete density of states located at the center of the bandgap.

Lord, Kenneth↗