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At least 55 records · Page 3

NASA-DoD Lead-Free Electronics Project. DRAFT Joint Test Report

The use of conventional tin-lead (SnPb) in circuit board manufacturing is under ever-increasing political scrutiny due to increasing regulations concerning lead. The "Restriction of Hazardous Substances" (RoHS) directive enacted by the European Union (EU) and a pact between the United States National Electronics Manufacturing Initiative (NEMI), Europe's Soldertec at Tin Technology Ltd. and the Japan Electronics and Information Technology Industries Association (JEITA) are just two examples where worldwide legislative actions and partnerships/agreements are affecting the electronics industry. As a result, many global commercial-grade electronic component suppliers are initiating efforts to transition to lead-free (Pb-free) in order to retain their worldwide market. Pb-free components are likely to find their way into the inventory of aerospace or military assembly processes under current government acquisition reform initiatives. Inventories "contaminated" by Pb-free will result in increased risks associated with the manufacturing, product reliability, and subsequent repair of aerospace and military electronic systems. Although electronics for military and aerospace applications are not included in the RoHS legislation, engineers are beginning to find that the commercial industry's move towards RoHS compliance has affected their supply chain and changed their parts. Most parts suppliers plan to phase out their non-compliant, leaded production and many have already done so. As a result, the ability to find leaded components is getting harder and harder. Some buyers are now attempting to acquire the remaining SnPb inventory, if it's not already obsolete. Original Equipment Manufacturers (OEMs), depots, and support contractors have to be prepared to deal with an electronics supply chain that increasingly provides more and more parts with Pb-free finishes-some labeled no differently than their Pb counterparts-while at the same time providing the traditional Pb parts. The longer the transition period, the greater the likelihood of Pb-free parts inadvertently being mixed with Pb parts and ending up on what are supposed to be Pb systems. As a result, OEMs, depots, and support contractors need to take action now to either abate the influx of Pb-free parts, or accept it and deal with the likely interim consequences of reduced reliability due to a wide variety of matters, such as Pb contamination, high temperature incompatibility, and tin whiskering. Allowance of Pb-free components produces one of the greatest risks to the reliability of a weapon system. This is due to new and poorly understood failure mechanisms, as well as unknown long-term reliability. If the decision is made to consciously allow Pb-free solder and component finishes into SnPb electronics, additional effort (and cost) will be required to make the significant number of changes to drawings and task order procedures. This project is a follow-on effort to the Joint Council on Aging Aircraft/Joint Group on Pollution Prevention (JCAA/JG-PP) Pb-free Solder Project which was the first group to test the reliability of Pb-free solder joints against the requirements of the aerospace and military community.

Kessel, Kurt↗

Lead-free solders: issues of toxicity, availability and impacts of extraction

This project set out to evaluate the critical issues of toxicity and public health effects, material availability, and the environmental impacts of raw material extraction and metal finishing, with the goal of using environmental impact as a factor in selecting feasible lead-free alloys.

toxicity lead-free solder packaging↗

Tunable broadband luminescence in lead-free hybrid copper halides

Metal halides are an important class of optoelectronic materials combining exceptional optical and electronic properties. An inherent advantage of metal halides is their solution synthesis and processability, which render them as low-cost and environmentally friendly materials for a range of applications from photovoltaics and photodetection to solid-state lighting (SSL). Here, in this study, we synthesized three previously unreported lead-free organic–inorganic hybrid copper halides: (OA) 4 CuX 5 (X = Br, I; OA + = C 8 H 17 NH 3+ , n-octylammonium cation) and (HA) 2 CuI 3 (HA + = C 6 H 13 NH 3 + , n-hexylammonium cation), all of which exhibit broadband emissions arising from self-trapped excitons (STEs). Among these compounds, (OA) 4 CuI 5 demonstrates tunable dual-band white-light emission with a high color rendering index value of 91 at room temperature. Temperature-dependent photoluminescence measurements and first-principles calculations reveal distinct behaviors between the two emission states in (OA) 4 CuI 5 . These findings highlight the potential of copper halide compounds for optoelectronic applications, particularly in the development of environmentally friendly solid-state lighting technologies.

36 MATERIALS SCIENCE↗

Lead-Free Organic–Perovskite Hybrid Quantum Wells for Highly Stable Light-Emitting Diodes

Two-dimensional perovskites that could be regarded as natural organic-inorganic hybrid quantum wells (HQWs) are promising for light-emitting diode (LED) applications. High photoluminescence quantum efficiencies (approaching 80%) and extremely narrow emission bandwidth (less than 20 nm) have been demonstrated in their single crystals; however, a reliable electrically driven LED device has not been realized owing to inefficient charge injection and extremely poor stability. Furthermore, the use of toxic lead raises concerns. Here, we report Sn(II)-based organic-perovskite HQWs employing molecularly tailored organic semiconducting barrier layers for efficient and stable LEDs. Utilizing femtosecond transient absorption spectroscopy, we demonstrate the energy transfer from organic barrier to inorganic perovskite emitter occurs faster than the intramolecular charge transfer in the organic layer. Consequently, this process allows efficient conversion of lower-energy emission associated with the organic layer into higher-energy emission from the perovskite layer. Thus, this greatly broadened the candidate pool for the organic layer. Incorporating a bulky small bandgap organic barrier in the HQW, charge transport is enhanced and ion migration is greatly suppressed. We demonstrate a HQW-LED device with pure red emission, a maximum luminance of 3466 cd m -2 , a peak external quantum efficiency up to 3.33%, and an operational stability of over 150 h, which are significantly better than previously reported lead-free perovskite LEDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing Light-Induced Microstrain and Phase Transition in Lead-Free Perovskites Using Time-Resolved X-Ray Diffraction

Metal halide perovskites have emerged as promising materials for optoelectronic applications in the last decade. A large amount of effort has been made to investigate the interplay between the crystalline lattice and photoexcited charge carriers as it is vital to their optoelectronic performance. Among them, ultrafast laser spectroscopy has been intensively utilized to explore the charge carrier dynamics of perovskites, from which the local structural information can only be extracted indirectly. Here, we have applied a time-resolved X-ray diffraction technique to investigate the structural dynamics of prototypical two-dimensional lead-free halide perovskite Cs 3 Bi 2 Br 9 nanoparticles across temporal scales from 80 ps to microseconds. We observed a quick recoverable (a few ns) photoinduced microstrain up to 0.15% and a long existing lattice expansion (~a few hundred nanoseconds) at mild laser fluence. Once the laser flux exceeds 1.4 mJ/cm 2 , the microstrain saturates and the crystalline phase partially transfers into a disordered phase. This photoinduced transient structural change can recover within the nanosecond time scale. Furthermore, these results indicate that photoexcitation of charge carriers couples with lattice distortion, which fundamentally affects the dielectric environment and charge carrier transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetizing lead-free halide double perovskites

Spintronics holds great potential for next-generation high-speed and low–power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs 2 Ag(Bi:Fe)Br 6 , Fe 3+ replaces Bi 3+ and forms FeBr 6 clusters that homogenously distribute throughout the double perovskite crystals. Furthermore, we observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.

36 MATERIALS SCIENCE↗

K 2 CuX 3 (X = Cl, Br): All-Inorganic Lead-Free Blue Emitters with Near-Unity Photoluminescence Quantum Yield

Recently, copper(I) halides have been gaining increased attention as highly luminescent nontoxic alternatives to lead halide perovskites for optoelectronic applications. In this paper, we report preparation of blue emitting, lead free, all-inorganic halides K 2 CuX 3 (X = Cl, Br) through five synthetic methods including traditional solid-state and solution methods. The photoluminescence (PL) emission spectra of K 2 CuCl 3 and K 2 CuBr 3 exhibit narrow peaks centered at 392 and 388 nm with full widths at half-maximum (fwhm) values of ~54 nm. The visible bright blue emission is corroborated by the remarkably high photoluminescence quantum yield (PLQY) values up to ~97%. Furthermore, radioluminescence measurements on K 2 CuCl 3 yield a bright peak at 404 nm under irradiation with X-rays at 200 kVp and 20 mA, which is optimal for use with PMTs and Si photomultipliers, suggesting a strong potential of this family for radiation detection applications. Based on our combined experimental and computational investigations, the origin of the efficient luminescence in K 2 CuX 3 is attributed to the high stability self-trapped excitons (STE) formed in the one-dimensional anionic ∞ 1 [CuX 3 ] 2– chains. Advantageously, K 2 CuX 3 demonstrate improved air- and photostability compared to the previously reported copper(I) halides. The discovery of highly efficient and high stability light emitters based on earth-abundant copper(I) halides paves the way for their potential practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Developing a NASA Lead-Free Policy for Electronics - Lessons Learned

The National Aeronautics and Space Administration (NASA) is not required by United States or international law to use lead-free (Pb-free) electronic systems but international pressure in the world market is making it increasingly important that NASA have a Pb-free policy. In fact, given the international nature of the electronics market, all organizations need a Pb-free policy. This paper describes the factors which must be taken into account in formulating the policy, the tools to aid in structuring the policy and the unanticipated and difficult challenges encountered. NASA is participating in a number of forums and teams trying to develop effective approaches to controlling Pb-free adoption in high reliability systems. The activities and status of the work being done by these teams will be described. NASA also continues to gather information on metal whiskers, particularly tin based, and some recent examples will be shared. The current lack of a policy is resulting in "surprises" and the need to disposition undesirable conditions on a case-by-case basis. This is inefficient, costly and can result in sub-optimum outcomes.

Sampson, Michael J.↗

Machine learning-enhanced design of lead-free halide perovskite materials using density functional theory

The investigation of emerging non-toxic perovskite materials has been undertaken to advance the fabrication of environmentally sustainable lead-free perovskite solar cells. This study introduces a machine learning methodology aimed at predicting innovative halide perovskite materials that hold promise for use in photovoltaic applications. The seven newly predicted materials are as follows: CsMnCl 4 , Rb 3 Mn 2 Cl 9 , Rb 4 MnCl 6 , Rb 3 MnCl 5 , RbMn 2 Cl 7 , RbMn 4 Cl 9 , and CsIn 2 Cl 7 . The predicted compounds are first screened using a machine learning approach, and their validity is subsequently verified through density functional theory calculations. CsMnCl 4 is notable among them, displaying a bandgap of 1.37 eV, falling within the Shockley-Queisser limit, making it suitable for photovoltaic applications. Here, through the integration of machine learning and density functional theory, this study presents a methodology that is more effective and thorough for the discovery and design of materials.

36 MATERIALS SCIENCE↗

Rashba effects in lead-free ferroelectric semiconductor [CH 3 PH 3 ]SnBr 3

Here, first-principles density functional theory computations are used to predict Rashba effects cofunctional with ferroelectricity in a recently synthesized lead-free hybrid organic-inorganic perovskite MPSnBr 3 (MP=methylphosphonium, [CH 3 PH 3 ] + ). The ground state of the material is polar monoclinic with calculated spontaneous polarization of 3.01 µC/cm 2 . It exhibits near band edges spin-splitting of up to 3.3 meV and Rashba coefficient up to 0.62 eV Å. The spin textures have different topology in the conduction and valence band, which originates from the difference in the spin-momentum coupling strengths. They occur in two orthogonal planes of the Brillouin zone and are coupled to the direction of spontaneous polarization. These features persist at a finite temperature of 293 K. At 333 K, that is above monoclinic to orthorhombic phase transition, spontaneous polarization is reduced to 0.15 µC/cm 2 , while the maximum spin splitting and Rashba coefficient reduce slightly to the value of 2.9 meV and 0.41 eV Å, respectively. The spin textures remain coupled with the polarization direction. We investigate the dependence of the aforementioned properties on the choice of computational methodology to extend the first-principles predictions to include finite temperature effects. We find that the predictions are sensitive to the methodology. Our study reveals the potential of MPSnBr 3 for low-temperature applications in spintronics and quantum computing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling functions for lead and lead-free neutron monitors from the latitudinal measurements performed in 1982 in the research station Academician Kurchatov

The latitudinal behavior of intensities and multiplicities was registered by the neutron monitor 2 NM and the lead-free neutron monitor 3 SND (slow-neuron detector) in the equator-Kaliningrad line in the Atlantic Ocean. Coupling coefficients for 3 SND show the sensitivity of this detector to primary particles of cosmic rays of energies on the average lower than for 2 NM. As multiplicities increase, the coupling coefficients shift towards higher energies.

Alekanyan, T. M.↗

Lead-Free Propellant for Propellant Actuated Devices

Naval Surface Warfare Center, Indian Head Division's CAD/PAD Department has been working to remove toxic compounds from our products for about a decade. In 1992, we embarked on an effort to develop a lead-free double base propellant to replace that of a foreign sole source. At the time there were availability concerns. In 1995, the department developed a strategic proposal to include a wider range of products. Efforts included such efforts as removing lead sheathing from linear explosives and replacing lead azide and lead styphnate compounds. This paper will discuss efforts specifically related to developing non-leaded double base propellant for use in various Propellant Actuated Devices (PADs) for aircrew escape systems. The propellants can replace their leaded counterparts, mitigating lead handling, processing, or toxic exposure to the environment and personnel. This work eliminates the use of leaded compounds, replacing them with a more environmentally benign metal-organic salt. Historically double-base propellants have held an advantage over other families of energetic materials through their relative insensitivity of the burning rate to changes in temperature and pressure. This desirable ballistic effect has been obtained with the use of a lead-organic salt alone or in a physical mixture with a copper-organic salt, or more recently with a lead-copper complex. These ballistic modifiers are typically added to the double-base 'paste' prior to gelatinization on heated calendars or one type or another. The effect of constant burning rate over a pressure range is called a 'plateau' while an even more beneficial effect of decreasing burning rate with increasing pressure is termed a 'mesa.' The latter effect results in very low temperature sensitivity of the propellant burning rate. Propellants with such effects are ideal tactical rocket motor propellants. The use of lead compounds poses a concern for the environment and personnel safety due to the metal's toxic nature when introduced into the atmosphere by propellant manufacturing, rocket firings, and disposal. Two separate programs are underway at Indian Head to replace the leaded ballistic modifiers in NOSIH-AA-2 and KU propellants. Although the system requirements were very different, the programs gained valuable information from one another throughout their course.

Goodwin, John L.↗

NASA-DoD Lead-Free Electronics Project

The primary technical objective of the project is to undertake comprehensive testing to generate information on failure modes/criteria to better understand the reliability of: Packages (e.g., TSOP, BGA, PDIP) assembled and reworked with lead-free alloys Packages (e.g., TSOP, BGA, PDIP) assembled and reworked with mixed (lead/lead-free) alloys.

Kessel, Kurt↗

Crystal structure and luminescence properties of lead-free metal halides (C 6 H 5 CH 2 NH 3 ) 3 MBr 6 (M = Bi and Sb)

Organic–inorganic hybrid metal halides have received extensive attention owing to their versatile structures and optoelectronic properties. Herein, we report two lead-free metal halides, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 [PMA + : (C 6 H 5 CH 2 NH 3 ) + , as the abbreviation of phenylmethylammonium], which possess iso-structural zero-dimensional structures and crystallize in the monoclinic space group P2 1 /c. (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit optical band gaps of ~3.50 and 3.40 eV, respectively, and density functional theory calculations reveal their indirect bandgap behaviors. Upon 350 and 425 nm excitation, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit broadband emission peaking at 510 nm and 625 nm with wide full-widths at half-maximum of ~153 and 175 nm, respectively. The emission mechanism of the metal halides is attributed to self-trapped exciton emission. The relationship between the crystal structure and luminescence intensity is also discussed. Lastly, both metal halides have high decomposition temperatures and are stable for long-term storage under ambient conditions, demonstrating their potential for optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultra broadband yellow emitting lead-free metal halide perovskite like compounds with near-unity emission quantum yields

Metal halide perovskites (MHPs) are interesting semiconductor materials with potential for use in optoelectronic and photonic devices. Their practical applications are hindered due to the negative environmental effects of the lead ions (Pb 2+ ) used in these materials and stability issues. Exploring new environmentally friendly materials with lead-free metal halides and investigating the factors affecting their optical properties and stability are essential. The broadband emission and high (near-unity; ~100%) photoluminescence quantum yield (PLQY) of low-dimensional copper(I) halides make them great candidates for the next-generation luminescent materials for lighting applications. Here, a Cu(I) iodide based organic/inorganic hybrid halide (benzo-15-crown-5) 2 NaH 2 OCu 4 I 6 (BCNCI) with a zero-dimensional (0D) cluster was prepared. The BCNCI has a broadband yellow emission peaked at 548 nm with a near-unity PLQY (99.1%) upon excitation at 365 nm (ultraviolet). Upon excitation at 450 nm (blue), a high PLQY of 82% was also achieved. The luminescence mechanism was discussed in detail. Interestingly, BCNCI exhibits ultra-broad band excitation in the 300–500 nm range, which matches commercially available UV and blue-emitting chips. Compared to commercial YAG:Ce 3+ phosphors, the emission spectrum is sufficiently broad to cover the visible spectral region. This work illustrates a good example of developing an environmentally friendly white light source, using high-performance copper halides with adequate broadband excitation and emission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Achieving giant electrostrain of above 1% in (Bi,Na)TiO 3 -based lead-free piezoelectrics via introducing oxygen-defect composition

Piezoelectric ceramics have been extensively used in actuators, where the magnitude of electrostrain is key indicator for large-stroke actuation applications. Here, we propose an innovative strategy based on defect chemistry to form a defect-engineered morphotropic phase boundary and achieve a giant strain of 1.12% in lead-free Bi 0.5 Na 0.5 TiO 3 (BNT)–based ceramics. The incorporation of the hypothetical perovskite BaAlO 2.5 with nominal oxygen defect into BNT will form strongly polarized directional defect dipoles, leading to a strong pinning effect after aging. The large asymmetrical strain is mainly attributed to two factors: The defect dipoles along crystallographic [001] direction destroy the long-range ordering of the ferroelectric and activate a reversible phase transition while promoting polarization rotation when the dipoles are aligned along the applied electric field. Our results not only demonstrate the potential application of BNT-based materials in low-frequency, large-stroke actuators but also provide a general methodology to achieve large strain.

36 MATERIALS SCIENCE↗

NASA DOD Lead Free Electronics Project

The primary'technical objective of this project is to undertake comprehensive testing to generate information on failure modes/criteria to better understand the reliability of: Packages (e.g., Thin Small Outline Package [TSOP], Ball Grid Array [BGA], Plastic Dual In-line Package [PDIPD assembled and reworked with lead-free alloys Packages (e.g., TSOP, BGA, PDIP) assembled and reworked with mixed (lead/lead-free) alloys.

Kessel, Kurt R.↗