Proposal submission instructions

(i) Small bandgap and large light absorption coefficient yields large amount of photo-generated electrons and holes.

(ii) Short light absorption length (~200 nm) requires only very thin layers of perovskite for light harvesting.

(iii) High electron-hole mobility and large electron-hole diffusion lengths make them excellent candidates for photovoltaic applications.

(iv) The low-temperature solution-based processes to prepare the perovskite allow the integration with flexible plastic substrates and other photovoltaic devices.

At present only limited results have been reported in the literature on performance of perovskite solar modules. All studies have focused on small lab-scale (~0.1 cm2) prototypes. Translating the lab-scale perovskite solar cells into low-cost large-scale production process is one of the major challenges in the development of perovskite solar modules. Therefore, the objective is to address this technology gap in the design and fabrication of perovskite photovoltaic modules for the intended integration.

Flexible modules may need to incorporate re-designed cell architecture to make them compatible with the synthesis process required for the flexible substrates (eg. 3D printing processes). Printing and casting processes may need to be developed for perovskites to allow layering with precise dimensions and desired interfacial characteristics. Investigations may also need to be conducted on multiple compositions under various environmental conditions to determine the optimum window for the module operation relevant to the wireless sensors and wearable electronics applications. Field testing may also need to be conducted to determine the failure and aging mechanisms of the modules, and strategies should be proposed to resolve the environmental degradation issues.

PHASE I: Complete the design of the architecture for a flexible perovskite module with an efficiency greater than 20% for wearable energy harvesting and wireless sensor nodes application and develop the fabrication procedures. Designs should include realistic material parameters. The flexible photovoltaic fabrication technique should be based on a low-temperature process. Analyze cost-competitive roll-to-roll printing process for mass fabrication of the flexible photovoltaic module. Provide preliminary experimental results on the feasibility of the proposed module architecture including bandgap-voltage offsets.

PHASE II: Develop a low-cost inorganic p-type semiconductor to replace the spiro-OMeTAD and integrate with the module architecture developed in Phase I. Address the hysteresis, thermal and humidity challenges and demonstrate a method to improve the lifetime. In addition to the heterojunction-induced built-in electric field as driving force to separate and transport the photo-excited electron-hole pairs, demonstrate the role of other effects in improving the efficiency. Demonstrate the wireless sensor node operation utilizing adequate size modules for a specific targeted defense application. Integrate the fabricated module up to 12 x12 area with a wearable and demonstrate the battery recharging capability under normal environmental conditions.

PHASE III DUAL USE APPLICATIONS: Demonstrate continuous roll-to-roll manufacturing of the developed modules and integration with the wearables and sensor nodes. Optimize the power conversion efficiency for flexible perovskite solar modules, the module geometries (such as stripe width, gap size, module length), and stability under various environmental conditions and strain. Develop packaging layers to provide adequate protection over the intended lifetime of the application. Focus should be on integrated product development and not on just the power source.

REFERENCES:

1. Dong, Y. Fang, Y. Shao, P. Mulligan, J. Qiu, L. Cao, and J. Huang, Science, Vol. 347, pp. 967-970 (2015).

2. W. Chen, Y. Wu, Y. Yue, J. Liu, W. Zhang, X. Yang, H. Chen, E. Bi, I. Ashraful, M. Gr’tzel, and L. Han, Science, Vol. 350, 944-950 (2015).

3. M. Yang, Y. Zhou, Y. Zeng, C.-S. Jiang, N.P. Padture, and K. Zhu, Adv. Mater., Vol. 27, 6363-6070 (2015).

4. X. Zheng, B. Chen, C. Wu, and S. Priya, Nano Energy, 17, 269-278 (2015).

KEYWORDS: energy harvesting, wireless sensor nodes, perovskite solar module

TECHNOLOGY AREA(S): Materials/Processes

The technology within this topic is restricted under the International Traffic in Arms Regulation (ITAR), which controls the export and import of defense-related material and services. Offerors must disclose any proposed use of foreign nationals, their country of origin, and what tasks each would accomplish in the statement of work in accordance with section 5.4.c.(8) of the Announcement.

OBJECTIVE: This STTR effort seeks to investigate novel approaches using multilayered hybrid 2-dimensional nanostructures as passive coatings and evaluate their interactions with high energy lasers.

DESCRIPTION: As part of the continuous transformation of the US Armed forces to be endowed with new, advanced and effective military capabilities it is an unequivocal paradigm to eradicate, minimize and mitigate vulnerabilities from them as well. The development of protection and hardening mechanisms against directed energy weapons such as high energy lasers are necessarily critical requirements for the progression of effective countermeasures [1]. High energy lasers (HELs) possess certain unique attributes such as speed of light response, precision strikes, reduced collateral damage, and potentially low cost per kill. They have the potential to cause damage or disable electronic components, sensors, optics, and structural components of advanced armaments, thereby disabling their effectiveness in completing intended missions. Many approaches, including chemical lasers, fiber lasers, solid state lasers, and free electron lasers, are available to build HELs, and many impediments to their deployment are steadily being overcome. Commensurate with the advances in HELs as directed energy weapons, it is imperative that parallel advances are required for protection against them, as well as to achieve an asymmetrical advantage over the adversaries. This topic endeavors, in particular, to research schemes for understanding fundamental high energy laser interactions with exploratory photonic material structures and designs.
PHASE I: Investigate novel approaches using multilayered hybrid 2-dimensional nanostructures as passive coatings and evaluating their interactions with high energy lasers. In particular, the aim is to design photonic designs of 2D metallic/inorganic/organic materials wherein disorder in the structure may be used to affect significant extinction and/or reflection of high energy coherent beams. In this regard, photonic glass with and without self-similar structures (fractals) could be advantageous as an additional variable to manipulate the incident radiation. At the end of Phase I, areas for further detailed investigation during Phase II should be identified.

PHASE II: Detailed physics based models will be developed for understanding the material interactions with high energy radiation using disorder in multilayered hybrid 2-dimensional nanostructures. Non-linear materials, photonic band structure designs, nanoporous compositions, self-similar structures, etc., can be considered as part of the design space. The design will also consider the effects of variables such as the angle of incidence, beam quality and polarization effects, if any, of the incident radiation. It can be assumed that the radiation is in the visible to near IR wavelength range with target irradiances in the range of tens to hundreds of kilowatts per cm2. Thin film material structures may be supported on appropriate substrates that take into account mechanical, thermal and other constraints. Fundamental material attributes will be developed for comparing the efficacy of the various nanostructure designs. Designs should be driven by final implementable solutions. The deliverables at the conclusion of the Phase II effort would include a fundamental understanding of the material interactions with high energy lasers.

REFERENCES:

1. Defense Science Board Task Force on Directed Energy Weapons, Office of the Under Secretary of Defense for Acquisition, Technology and Logistics, Washington D.C. Dec. 2007.

2. A. F. Koenderink and W. L. Vos, “Optical properties of real photonic crystals: anomalous diffuse transmission,” J. Opt. Soc. Am. B, 22, 1075-1083, 2005.

3. J.A. Bossard, L.Lin and D.H. Werner ”Evolving random fractal Cantor superlatttices for the infrared using a genetic algorithm,” J. R. Soc. Interface 13, 0975, 2015.

4. V.M. Shalaev, ed. Optical properties of nanostructured random media. Vol. 82. Springer Science & Business Media, 2002.

TECHNOLOGY AREA(S): Chemical/Biological Defense

The technology within this topic is restricted under the International Traffic in Arms Regulation (ITAR), which controls the export and import of defense-related material and services. Offerors must disclose any proposed use of foreign nationals, their country of origin, and what tasks each would accomplish in the statement of work in accordance with section 5.4.c.(8) of the Announcement.

OBJECTIVE: Explosive & chem-bio (CB) sensors are necessary to provide situational awareness and early warning against threat events from homemade explosives and weapons of mass destruction (WMD), to protect personnel and assets in missions ranging from integrated base defense to forward operating bases and reconnaissance. The Department of Defense is interested in reducing costs, labor, and footprint while enhancing situational awareness and early warning to compress the time from threat event to commander decision. Small, low-cost, autonomous sensors are needed for modular, self-scaling, persistent, “layered" surveillance networks. There is a desire to develop a sensor in a functional form similar to a smoke alarm. A smoke alarm exists in a small package and can run for more than a year on a single 9 volt battery. Low power and low profile are very desirable characteristics.

Recent innovations in additive manufacturing and smart materials are expected to enable innovative sensor concepts and designs that enhance sensitivity, selectivity, increase monitoring performance and coverage at reduced costs, size, weight, power, with integrated printed communication architecture. Integrated printed communication hardware will provide a path forward to inexpensive networking of energetic & CB sensors, with sensors and communications hardware integrated onto a single monolithic structure.

A design in which the sensor and communications are printed or placed onto a monolithic structure will provide “surge" capabilities. Currently, threat sensors, along with communications and power supplies, are stockpiled in advance, adding to an already overburdened logistical stream. The ability to rapidly manufacture “on-demand" will provide rapid, reliable replacement of sensing elements to DoD personnel without the need for large stockpiles of materiel. There may even be the possibility of providing manufacturing capabilities in the field. Some current technologies that detect and identify explosive & CB threats involve technologies that are expensive and difficult to maintain. Examples include LIDARS, FTIR (Fourier transform infrared spectrometers), Ion Mobility Spectrometers (IMS), molecular assays. Alarm (presumptive) states can be given by sensors that provide element analysis (AP2C), M8 paper, colorimetric arrays and immunoassays. IMS technology has been incorporated into a handheld ion mobility spectrometer that has seen recent improvements in size/weight reduction, but still requires logistics support for lithium ion battery replacements. The initial outlay for M8 paper is very low, but when used to monitor an area over time, has a high labor load for replacement and visual inspection.

DESCRIPTION: Explosive & chem-bio (CB) sensors are necessary to provide situational awareness and early warning against threat events from homemade explosives and weapons of mass destruction (WMD) to protect personnel and assets in missions ranging from integrated base defense to forward operating bases and reconnaissance. The Department of Defense is interested in reducing costs, labor, and footprint while enhancing situational awareness and early warning to compress the time from threat event to commander decision. Small, low-cost, autonomous sensors are needed for modular, self-scaling, persistent “layered" surveillance networks. There is a desire to develop a sensor in a functional form similar to a smoke alarm. A smoke alarm exists in a small package and can run for more than a year on a single 9 volt battery. Low power and low profile are very desirable characteristics.

Recent innovations in additive manufacturing and smart materials are expected to enable innovative sensor concepts and designs that enhance sensitivity, selectivity, increase monitoring performance and coverage at reduced costs, size, weight, power, with integrated printed communication architecture. Integrated printed communication hardware will provide a path forward to inexpensive networking of energetic & CB sensors, with sensors and communications hardware integrated onto a single monolithic structure.

A design in which the sensor and communications are printed or placed onto a monolithic structure will provide “surge" capabilities. Currently, threat sensors, along with communications and power supplies, are stockpiled in advance, adding to an already overburdened logistical stream. The ability to rapidly manufacture “on-demand" will provide rapid, reliable replacement of sensing elements to DoD personnel without the need for large stockpiles of materiel. There may even be the possibility of providing manufacturing capabilities in the field. Some current technologies that detect and identify explosive & CB threats involve technologies that are expensive and difficult to maintain. Examples include LIDARS, FTIR (Fourier transform infrared spectrometers), Ion Mobility Spectrometers (IMS), molecular assays. Alarm (presumptive) states can be given by sensors that provide element analysis (AP2C), M8 paper, colorimetric arrays and immunoassays. IMS technology has been incorporated into a handheld ion mobility spectrometer that has seen recent improvements in size/weight reduction, but still requires logistics support for lithium ion battery replacements. The initial outlay for M8 paper is very low, but when used to monitor an area over time, has a high labor load for replacement and visual inspection.

PHASE I: Use additive manufacturing to develop an energetic & CB threat sensor that has a very small profile and can operate using very little power. The system should be able to run for an entire year using a single 9 volt battery, similar to a smoke detector. Develop five (5) printable sensor designs using additive manufacturing methods and materials that can detect and discriminate between homemade explosives such as triacetone triperoxide (TATP) and hexamethylenetriperoxidediamine (HMTD) or simulants thereof, such as ditertiarybutylperoxide, and CB threats such as methyl salicylate, ethanol, ammonia, and acetic acid. Design concepts can include one fiber/patch/print per analyte or can include multiple detection capabilities within a single fiber/patch/print. A design concept may include using printed structures and materials to exclude and narrow selections through pathways down or along the sensor to enhance selectivity. The design concepts should also be developed to address sensing sensitivity and selectivity. Designs should address rapid, on-demand-type additive manufacturing that has the potential to reduce stockpiling of sensor elements while still maintaining the ability to rapidly respond to a “surge" in demand. Monolithic designs that incorporate sensing elements, communications, and power are desirable.

Concept and design simulations should demonstrate a detection Objective (O) of 5-10 parts per billion (ppb), detection Threshold (T) 5-10 parts per million (ppm), time to detection of 1-5 seconds from time analyte contacts the presenting surface face, low power requirements that would enable 9v battery life of at least one year, a payload weight (including battery) of less than 5-10 grams (suitable for micro-UAS paylod or helmet/uniform patch), an integrated reporting communication capability (e.g., a printed RFID tag). A low cost testing apparatus should also be developed to characterize sensor performance against challenge analytes. Concepts that include self-calibration approaches for autonomous, low/no power, self-check are desirable. Offerings that include novel, non-commercial materials (e.g., specialty inks) should include an assessment for maturity and availability of the materials (technical and procurement risk assessment). Offerings that include the predictive design simulations and/or an early feasibility print with preliminary characterization test data are considered of high value. Proposals offering to do a “market survey" as the sole Phase I task to identify candidate technologies for down selection and a design developed in Phase II will be considered non-responsive.

PHASE II: Fabricate prototype sensors based on the Phase I design and findings. Characterize the sensors and demonstrate performance metrics listed in Phase I. Identify key performance metrics needed that can be used to guide further sensor development. Some example metrics may include, but are not limited to, rheological properties, viscosity, dielectric properties, resistance/impedance.

The Final Report should include (1) engineering and materials designs (2) methods and processes used to make materials, (3) fabrication/printing methods used, (4) test report, testing methods, data collection and data analysis, (5) approaches and risks for manufacturing scale-up, maturity and technical risks, (6) anticipated production costs for sensors and the relevant component materials and inks, (7) lessons learned.

Deliverables should include 5 complete sensor sets and Final Report.

PHASE III DUAL USE APPLICATIONS: Further research and development during Phase III efforts will be directed towards refining deployable sensors based on results from modeling and testing conducted during the Phase II effort and integrating them into Army and Joint Service persistent surveillance networks and layered sensing networks. Improvements to communications features will be a focus so that the sensors can meet U.S. Army CONOPS and end-user requirements.

REFERENCES:

1. Michael G. Campbell, Sophie F. Liu, Timothy M. Swager, and Mircea Dinc, “Chemiresistive Sensor Arrays from Conductive 2D Metal-Organic Frameworks," J. Am. Chem. Soc., 2015, 137 (43), pp 13780-13783

2. Srikanth Ammu, Vineet Dua, Srikanth Rao Agnihotra, Sumedh P. Surwade, Aksah Phulgirkar, Sanjaydumar Patel, and Sanjeev K. Manohar, “Flexible, All-Organic chemiresistor for Detecting Chemically Aggressive Vapors," Journal of the American Chemical Society, 2012, 134, pp 4553-4556

3. E. Skotadis, Jun Tang, V. Tsouti, D. Tsoukalas, “Chemiresistive sensor fabricated by the sequential ink-jet printing deposition of a gold nanoparticle and polymer layer," Microelectronic Engineering, 2010, 87, pp 2258-2263

4. Valery R.Marinov, Yuriy A. Atanasov, Adeyl Khan, Dustin Vaselaar, Aaron Halvorsen, Doughlase L. Schulz, Douglas B.Chrisey, “Direct-write vaport sensors on FR4 plastic substrates," IEEE Sensors Journal, June 2007, VOL 7, No. 6, pp 937-944

5. Richard J. Roush and Susan L. Roush, “Airborne hazard detector", U.S. Patent Number 6895889, May 24, 2005

6. S.Y.H. Tang and J.T.S. Chan, “A review article on nerve agents", Hong Kong Journal of Emergency Medicine, Volume 9 Number 2, pages 83-89, April 2002.

7. Kimberly A. Barker and Christina Hantsch Bardsley, “Blister Agents, in Toxico-terrorism: Emergency Response and Clinical Approach to Chemical, Biological, and Radiological Agents," Robin McFee and Jerrold Leikin (editors), pages 261-268, McGraw-Hill Companies, 2007.

8. Michael Schwenk, Stefan Kluge and Hanswerner Jaroni, “Toxicological aspects of preparedness and aftercare for chemical-incidents", Toxicology, Volume 214, Issue 3, Pages 232-248, October 2005.

9. C.K. Cowan and P.D. Kovesi, “Automatic sensor placement from vision task requirements" in IEEE Transactions on Pattern Analysis and Machine Intelligence, Volume 10, Issue 3, pages 407-416, May 1988.

10. R.R. Brooks, C. Griffin, and D.S. Friedlander, “Self-organized distributed sensor network entity tracking", International Journal of High Performance Computing Applications, Volume 16, number 3, pages 207-219, 2002.

KEYWORDS: Chemical Biological Warfare Agent, homemade explosives (HMEs), vapor, aerosol, sensor, detection, identification, selectivity, sensitivity, low cost sensors, additive manufacture, 3D printing, conducting polymers, 2D materials, graphene, colorimetric, molecular printing.

A17A-T005

TITLE: Mid-Infrared Chip-scale Trace Gas Sensors

TECHNOLOGY AREA(S): Chemical/Biological Defense

The technology within this topic is restricted under the International Traffic in Arms Regulation (ITAR), which controls the export and import of defense-related material and services. Offerors must disclose any proposed use of foreign nationals, their country of origin, and what tasks each would accomplish in the statement of work in accordance with section 5.4.c.(8) of the Announcement.