Pathway for All Transparent Vertical Optical Devices Romualdo Alejandro Ferreyra, Ph.D. Period of Performance: 3 MonthsBackground During the last three decades, developments in the field of group III nitrides have been spectacular, with major breakthroughs which took place in the 1990s. They have been viewed as a highly promising material system for electronic and optoelectronic applications. As members of the group Ml nitrides family, AIN and GaN and their alloys with InN are all wide-bandgap materials (except for InGaN with very high In content) and can crystallize in both wurtzite and zincblende polytypes. The bandgaps of the wurtzite polytypes are direct and range from a possible value of ~ 0.8 eV for InN, to 3.4 eV for GaN, and to 6.1 eV for AIN. GaN alloyed with AIN and InN may span a continuous range of direct-bandgap energies throughout much of the visible spectrum, well into ultraviolet (UV) wavelengths. This makes the nitride system attractive for optoelectronic applications, such as light-emitting diodes (LEDs), laser diodes (LDs), and UV detectors". ‘Commercialization of bright blue and green LEDs and the possibility of yellow LEDs paved the way for developing full-color displays. Ifthe three primary-color LEDs, including red, produced by the InGaAIAs system are used instead of incandescent light bulbs in some form of color-mixing scheme, they would provide not only compactness and longer lifetime, but also lower power consumption for the same luminous flux output. Additional possible applications include use in agriculture as light sources for accelerated photosynthesis, and in health care for diagnosis and ‘treatment. Unlike display and lighting applications, digital information storage and reading require coherent light source because the diffraction limited optical storage density increases approximately quadratically with decreasing wavelength. The nitride material system, when adapted to semiconductor lasers in blue and UV wavelengths, offers increased data storage density, possibly as high as 50Gb per dise with 25 Gb promised soon in the blu-ray system. Other equally attractive applications envisioned include printing and surgery. When used as UV sensors in jet engines, automobiles, and fumaces (boilers), the devices wouid allow optimal fuel efficiency and effluent control for cleaner environment. Moreover, visible blind and solar-blind nitride-based photodetectors are also an ideal candidate for a number of applications including early missile- plume detection, UV astronomy, space-to-space communication, and biological effects On the other hand, recently, metal oxides such as GasOs, indium tin oxide (ITO), and ZnO have expanded their applications from transparent conducting oxides (TCO) to new fields as the growth technology advances. Instead of being used only as electrodes, these materials have been grown as single crystals through various growth techniques and applied to various fields including transparent semiconducting oxides (TSOs)."" Especially, GazO3 has attracted increasing interest because it can have different polymorph forms of a-, B-, 7-8, & and x-, depending on its crystal structure and the number of Ga ions. The wide bandgap and high breakdown field of GayOs have also expanded its potential for photoelectric devices, chemical sensors, photoelectrodes for photoclectrochemical (PEC) water splitting and others." In every semiconductor photodetector, a stack of semiconductor layers is deposited on a suitable substrate to build up a semiconductor photodetector. The p-i-n photodetector varieties formed by 1 petype, an intrinsic (tunable absorption region), and an n-type semiconductor layers operated near zero bias results in high quantum efficiency, low-frequency noise, and high detectivity, with a gain of I. In a photodetector, the light to be sensed must be able to reach and pass through the absorption region, which can be achieved by opening windows in the ohmic contacts or by depositing very thin semitransparent metallic film. However, these two techniques drop device performance, ie., cause current crowding and sensitivity. On the other hand, in the case of ba illuminated photodetectors the substrate needs to be polished to be transparent for the light to be detected" (see Fig. 1 a)). These restriction and limitation would be overcome with the continuoustunable range of direct-bandgap energies throughout the visible spectrum, well into ultraviolet (UV) wavelengths with the additional characteristic that the GaN alloys grow in a more direct way than oon the sapphire which is the material of choice for back-illuminated photodetectors, and also with the UV conductivity transparency of Ga2Os and indium tin oxide (ITO) ™. Material properties will allow us to implement all Transparent Vertical Optical Devices, in particular photodetector whit is the topic of the proposed project (see Fig. | b)) b) p-type material Absorption { Ito Current crowding TWAU Figure 1 Optical device implementation. a)standard , b) vertical proposed one. Objectives ‘The goal is to implement a vertical al transparent p-i-n photodetector based on the GaN alloys and ‘TSOs materials. With a design capable to respond from visible spectrum to well into ultraviolet (CY) wavelengths. With tunable response by selecting GaN alloy composition, and. the implementation of n-type region by using a n-GazOs substrate. And p-type region formed by “strain” doped heterointerfaces between ALO; and GazOs For this the following objective need to be attained: 1 GaN alloy growth on n-GaOs jrowth of GazOs on GaN alloy 3 — Deposition of multiple GaOvAbOs heterostructure on GaxOs Methodology The methodology to achieve the aims of the project is as follows. In order to grow GaN alloy on 1n-GarOx substrates, metal-organic vapor phase epitaxy (MOCVD) will be used. Access to MOCVD system is crucial for this project. After finding the best conditions for AIGAN (-50% Al for UV applications) growth on n-GaOs substrates, the grown material will be characterized to ensue its crystal and electrical characteristics are the correct ones for the implementation of the material as absorber material. To characterize the material, atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Photoluminescence (PL) techniques will be used to access material quality. The GaN alloy will vary in its composition, ic, aluminum percentage, according to the wavelength to be detected by the photodetector. Then one will be able to find appropriate condition for GaxOn growth on already grown GaN alloy, The next step is togrow ALOson GasOs forming a GaOx/ALOs heterostructure in order to implement p-type “strain”-doped heterointerfaces between AlOs and GayOs, where the piezoelectric field can induce a 2D hole gas at the interface, The p-type conductivity of fabricated heterostructures will be evaluated via magnetotransport. At this point, the functional structure of the photodetector is completed. Realization of the metal contact will be carried out by growing ITO thin film on top of Ga:Ox/ ALOs heterostructure and on top of ITO a Ti/Ni metal stack will be deposited by E-beam evaporation, ‘Then metal contact on the back side of the n- GaaOs substrate will be implemented by deposition of TWNi metal stack by E-beam evaporation. All Oxide will be grown by MOCVD. And metal stack will be pattemed by optical photolithography and acetone lift-off. Resulting p-i-n photodetector will be characterized by FV curves and tested with laser diode and photodetector bench, A ao a-- ‘Stating Materia Maal conta {GaN Alloy Grown ype sran-opes hotrontorocea Figure 2, Fabrication process illustration of p-n junctions Ga20s photodetector. Sig Forming functional heterostucture is a very active area of material science and electronic and optoelectronic devices. New materials and their use are always welcome for material scientists trying to understand the fundamental mechanisms that foster the formation of material, and electronic engineers are always eager to arrange materials that result in devices which perform better than the ones already exist. This project touches hot topic in material science like growing GaN alloys on Ga,Os substrates, which is interesting not only for photodetector but also for implementation of LEDs. Also the project will deal with the GaOx/AbOs heterostructure technology to implement p-type heterostructure for p-type contacts always necessary for bipolar devices, in particular, for optoelectronics ones. From the development of the photodetector it is expected to find new insights in the area of material growth and optoelectronic device design which will be beneficial to the material science and electronic communities. Photodetectors are of relevant importance in UV sensing in jet engines, automobiles, and furnaces, ‘The devices would allow optimal fuel efficiency and effluent control for cleaner environment, Invisible blind and solar-blind nitride-based photodetectors are also an ideal candidate for a number of applications e.g. UV astronomy, space-to-space communication, and biological effects. In this regards, UV sensor would be very beneficial to monitor UV solar radiation, especially, UVA and UVB, which are dangerous for human health. In particular, in summer in Argentina, UV radiation is quite strong because of ozone layer thinning. Also, UV has a negative effect on plantations. This is a topic of utmost concer in an agricultural country like Argentina, Therefore,‘counting with a tool as tunable UV photodetector will help monitor UV radiation to prevent its clinical effect on eyes and skin, and also help correlate UV radiation and its effects on plants grown in open areas. From the viewpoint of my own professional development, this project will help me deepen my knowledge in the area of optical devices through collaboration with other researchers. This is a very good opportunity to keep networking and make new friends for my future research, Evaluation and Dissemination This will be a single-institution project, so there will low overhead associate with teaming and ‘management. Weekly intemal project group meetings will be held to review the progress of the project and coordinate the work needs to be done. Written reports will also be prepared intemally on ‘a monthly basis. At the end of the stay (3 months), these will be compiled into a final report to be presented before whom it may concem, Promising results are expected to be published in a top intemational publication. Also, in my home country, the research results are expected to be presented at an annual meeting of the Associacion Argentina de Fisica (AFA) and in the Electronic Devices Course Iam teaching, Justification for Residence in the United States for the Proposed Project To successfully develop the proposed photodectector, a good deal not only of equipment and facilities but also of expertise especially in the area of material growth are needed. Also, a critical piece of equipment, a MOCVD, is vital for the project. At present, this equipment is not available in Argentina, and there is not any MOCVD capable to grow GaN semiconductors compounds in any laboratory of CONICET or Argentinean Institutions. The chosen place, Center for Quantum Devices (CQD) at Northwestem University directed by Professor Manijeh Razeghi, possesses all equipment, facilities, and know-how necessary to successfully complete the project. The primary facilities are available at the CQD to carry out the design, material growth, any required material characterization, the device processing, and device testing and analysis. The Center facilities include 3,000 square feet of clean room space, multiple MOCVD and MBE reactors, and a complete suite of material characterization equipment. The cleanroom at northwestern is equipped with a complete state-of-the-art high-purity hazardous gas handling system as well asa full hazardous gas monitoring system. An additional 3,500 square foot general laboratory space is also available for device testing. This facility meets all environmental Jaws and regulations of federal, state (inois), and local governments for airbome emissions, waterbome effluents, extemal radiation levels, outdoor noise, solid and bulk waste disposal practices, as well as the handling and storage of toxic and hazardous materials. Details of the specific equipment available at the facilities that will be used to complete the proposed work are as follows: A commercial AIXTRON (AIX 200/4) horizontal low-pressure MOCVD system is dedicated to growth of IIlNitride and Ga.0s materials. This reactorhas 14 sources and allows for great flexibility in heterostructure and bandgap engineering. It has the capability to operate from 5 to 1000 mbar and ‘can be inductively heated at temperatures up to 1600 °C. These high growth temperature and low growth pressure capabilities allow much more flexibility than conventional MOCVD systems A rotating 4 inch susceptor ensures uniform layers, Multiple organometallic, hydride, and oxygen sources are available to grow GaN alloys, GazOs, and AkOs materials. TetraEthyITin, Silane, and Bis(cyclopentadienyl)magnesium are also available to dope these layers. An inert glove box7S MOCVD reactors 12. MIE recone Xo ditacomcter a “fone elanred boa | SAR TL TTPL topo VE in Opt parvine Physics Ts ‘Chemistry Material Science Mechanical Engineering —s Electrical Engineering ican ang mal opr Bio Engineering cv + Opti boggy + Eta Io rapy pole bet Sos 7 Figure 3. Summary of the facilities available at the Center for Quantum Devices (COD) ensures reproducible results and helps maintain high uptime for this system by allowing routine maintenance and cleaning to be performed without exposing the system to ait. The structural material characterizations are performed using a high-resolution Phillips x-ray diffractometer with a copper Kai source and germanium monochromator as well as a BEDE triple- axis system that allows spatial wafer mapping and reciprocal space mapping. Surface characterization is completed using several optical Nomarski microscopes, a Hitachi $4500 scanning electron microscope with EDX capabilities, an atomic force microscope, a Tencor Instruments 2D surface profiler, and a new Zygo 3D interferometric surface profiler. An ellipsometer is used to characterize the optical properties of thin films, including refractive index, reflectivity and absorption. Instrumentation for optical characterization of the structures includes an ultraviolet-to-visible photoluminescence set-up using an Ar-P excimer laser (.=193 nm), frequency-doubled CW argon ion laser (.=244 nm), and a CW helium-cadmium laser (=325 nm). ‘An FTIR that covers the entire spectral range fiom 200 nm to>500 jim is available to characterize the intersubband absorption of III-Nitride structures. The electrical characterizations will mainly be performed using Hall effect measurements. Capacitance voltage (CV) may also be performed to extract additional electrical properties of the epitaxial films. A scanning electrochemical CV system allows us fo create profiles of the doping in complex structures, Processing and support facilities for devive fabrication include a number of fume hoods for sample preparation, general chemical processing and photolithographic processing. Two Karl Sus contact mask aligners are available for laser fabrication one with micrometer resolution, and a second aligner with sub-micron resolution and wafer back-side alignment capabilities. A holographiclithography system and an electron beam lithography system are available for the custom fabrication of nanostructures in semiconductor materials or photonic crystals. ‘The etching of device structures will be performed using either wet chemical etching, an electron cyclotron resonance reactive ion dry etching system (ECR-RIE), or a new inductively coupled plasma (ICP) dry etching system capable of creating highly vertical features. A rapid thermal annealing system isused forthe annealing of metal contacts. A plasma enhanced chemical vapor deposition (PECVD) and an ion beam sputtering systems are used to deposit high density dielectric films. Two dicing (or diamond-wheel sawing) systems are available for the realization of controlled, fine, and accurate cuts into semiconductor walers. A thermal evaporator and three electron-beam evaporators are used to deposit vatious metals onto semiconductor films including indium for packaging applications and metals for the realization of ohmic contacts. Die-bonding of processed ‘chips to submounts or chip carriers can be performed using semi-automatic die bonding Duration For safety reasons and for a good used of facilities and equipment need to be operated, a minimal period of training is required. During this time, it is expected to get familiar with the many ‘operational aspect of the processes necessary to realize the photodetector. Also, some of the time will be dedicate to the group meetings and discussions with Professor. Manijeh Razeghi. Because ‘endeavor will deal with technical aspects one needs to be familiar with before the implementation of the photodetector. It is reasonable to expect to perform several interactions of the whole process involved, before to attain satisfactory results. Furthermore, in experimental implementation of devices a second run is usually necessary to improve their performance. A tentative schedule would be as follow. Tem 1 Month 2 Month 3° Month 1) trains = 2_| GaNgrowth =T= 3_| G20 growth = 4 AOS growth = 3 _| Device Fabrication = © _| 2105 second ran =T=T=1 = T= 7_[ Finalrreport =Bibliography ‘FH, Morkog, Handbook of Nitride Semiconductors and Devices, vol. 1: Materials Properties, Physies and Growth, Wiley-VCH Verlag GmbH & Co, KGaA, 2009. *P, Ruterana, M. Albrecht, J. Neugebauer (Eds.), Nitride Semiconductors Handbook on Materials and Devices, Wiley-VCH Verlag GmbH & Co. KGaA, 2003, “A, E, Romanov, S, I. Stepanov, V. I. Nikolaev, and V. E. Bougrov, “Gallium Oxide: Properties and Applica 4 98 a Review.” Rey. Adv. Mater. Sci, vol. 44, pp. 63-86, 201 © K, Sasaki, M. Higashiwaki, A. Kuramata, T. Masui, and S. 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