Paper received: 2011-12-20, paper accepted: 2012-03-21 © 2012 Journal of Mechanical Engineering. All rights reserved. Nanotechnological Enhancement of Infrared Detectors by Plasmon Resonance in Transparent Conductive Oxide Nanoparticles Zoran Jaksic1* - Momcilo Milinovic2 - Danijela Randjelovic1 1 Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Serbia 2 Faculty of Mechanical Engineering, University of Belgrade, Serbia We investigated the use of plasmonic nanotechnology to enhance the performance of semiconductor infrared detectors. An increase of quantum efficiency, responsivity and specific detectivity is obtained by applying transparent conductive oxide (TCO) nanoparticles onto the surface of a photodetector. To this purpose we considered uncooled mercury cadmium telluride (HgCdTe) photoconductive detectors fabricated by isothermal vapor phase epitaxy but the same procedure can be applied to cryogenically cooled devices, including those of photovoltaic type. The main mechanism of enhancement is light concentration ensured through localized plasmon resonance at the TCO nanoparticles and through enhanced scattering, while the desired wavelength range is reached by a further redshifting through the adjustment of nanoparticle properties. The improvement can be implemented during the final stages of production of the existing photovoltaic and photoconductive detectors. The method is applicable to various practical applications, including updating of high-precision guided ammunition. Keywords: nanotechnology, homing head, infrared detectors, plasmonic enhancement, transparent metal oxides, nanoparticles 0 INTRODUCTION The possibility of detecting and recognizing objects under low light conditions [1] has applications in many fields, from personal and instrumental surveillance to homing devices utilizing heat seeking guidance. Advanced technological solutions for missile guidance provided in the past have later spread not only to missiles but also to classic projectiles like mortar shells, gun shells, etc., thus forming the basis for "smart ammunition". Single-shot lethality is becoming the most important quality requirement for both missiles and guided projectiles. New mortar shells technology [2] and [3], developed in the form of missiles with homing heads, usually depends either on laser illumination of the target for its guidance or an autonomous self-guided heat-seeking mode, as in the case of terminal infrared homing. When using terminal guidance for projectiles the main goal is to develop the recognition of signals reflected from illuminated targets, to hit and kill, to a level of a reliable technical characteristic in the required chain. This is especially important for fighting any type of combat armored targets in motion, which requires target tracking by laser designator during the projectile terminal approaching phase. The sensor on the homing head of a guided projectile requires highly sensitive optical detection to recognize reflected laser signals from the target illuminated by a designator and to provide an appropriate signal for the flight control correction of the missile or projectile. The control of the missile or the projectile at the last phase of ballistic trajectory at distances less than 1000 m requires fast influence on the changes of the missile's axes or velocity vector direction toward the mobile target. For this type of control [3] the element with the largest influence on the missile shooting performances is the type of detector in the homing head, which has to be sufficiently sensitive to measure the flux and the direction of the light impulse reflected from the illuminated target. The whole process is extremely rapid and the reaction of the homing head and the missile control mechanism directly influence target shooting errors. Since artillery projectiles [3] must be low-cost, compact, rugged and simple, this means that the implementation of the detection function must be performed without additional complex equipment for improving the sensitivity of light flux detection in the homing head sensor. Self-guidance homing heads operate without illumination sources and use infrared (IR) signature of targets to recognize the guidance LOS (line of sight) direction. This means that high response speed and high sensor sensitivity under poor lighting condition and at infrared wavelengths where, typically, the influence of noise and interference is much larger than in visible and further increases with wavelength, must be ensured. It is well known that semiconductor infrared detectors typically ensure the highest response speed of all detector types [1] and [4]. They do not depend on thermal diffusion at all, contrary to the thermal detectors, but are excited directly by infrared radiation from the target through interband transitions of charge carriers. Such direct conversion from light to electric signal ensures rapid reaction and because of that such detectors are the devices of choice in military systems. Another issue is how to improve the sensitivity (responsivity) and specific detectivity of infrared detector without simultaneously increasing the system complexity and cost. To this purpose one has to ensure a maximization of light flux within the active area of the detector. This belongs to the field of light management, which is one of the most significant issues with photodetectors generally, regardless of the wavelength range. It is of especial importance for the new homing heads utilizing either laser-illuminated or self-guided missiles and projectiles technology [2] and [3]. The aim of this paper is to present a possible nanotechnological solution for highly sensitive and low-cost infrared semiconductor detectors applicable for various purposes, including updating high-precision guided ammunition. To this purpose, mercury cadmium telluride uncooled photoconductive detectors fabricated by vapor phase epitaxy were considered. Aluminum-doped zinc oxide and tin oxide nanoparticles fabricated by nonaqueous procedure were considered for the improvement of detector samples. The original research results also include the assessment of the optimization wavelength range through redshifting of nanoparticle optical properties. 1 REQUIREMENTS AND CONSTRAINTS FOR INFRARED DETECTORS Active infrared systems, including those for homing heads, utilize as their main principle the detection of infrared radiation, usually at wavelengths belonging to the (3 to 5) mm or (8 to 14) mm atmospheric windows. The infrared photodetectors typically used for these ranges are either silicon thermal devices like bolometers, thermocouples, etc. (low-end and slower, but less expensive), or semiconductor detectors utilizing narrow-bandgap materials like indium antimonide or mercury cadmium telluride (much higher performance, a typical choice for military applications). Semiconductor devices offer much higher speeds, high specific detectivities with background-limited infrared photodetector (BLIP) operation and sharply defined operating wavelength ranges. Our present analysis is dedicated to this type of detectors. Mercury cadmium telluride (Hg1-xCdxTe, MCT) has been the infrared semiconductor material of choice for the last few decades [4]. The possibility to tailor its cadmium molar fraction x during fabrication and thus to design a desired cutoff wavelength makes it useful for various detection ranges, from near to far infrared. The most sensitive Hg1-xCdxTe infrared detectors are the cryogenically cooled ones [1], typically by liquid nitrogen or possibly by multi-stage thermoelectric coolers. However, there is also a class of Hg1-xCdxTe infrared photodetectors that operate at room temperature, furnishing specific detectivities in excess of 108 cmHz1/2/W [5]. Fabrication of these Hg1-xCdxTe infrared photodetectors using isothermal vapor phase epitaxy (ISOVPE) is presented in [6] and by liquid phase epitaxy (LPE) in [7]. It is well known that the performance of an infrared detector is described by its sensitivity and specific detectivity [1]. Sensitivity (also denoted as responsivity) is defined as a ratio of the incident infrared flux and the useful signal, which may be either voltage or current. The specific detectivity is further defined as the product of sensitivity and the squared active area divided by detector noise equivalent power. All of the exploitation demands quoted in the Introduction practically require the maximization of the specific detectivity in order to ensure the photodetector operation under weak illumination condition. On the other hand, this signifies there is a necessity to trap the maximum amount of the useful signal within the active region of the photodetector in order to optimize sensitivity (light management within the detector). This condition is especially important if the detector active areas are thin, as is usually the case with both ISOVPE and LPE epitaxial layers, but also for other devices from different materials and for other wavelength ranges, including e.g. ultrathin-film solar cells. Various strategies have been developed to improve the light concentration within the photodetector, including the use of immersion lenses, antireflection coatings and structures, surface reliefs, highly reflective detector back sides, etc. [8]. Among the most recently proposed methods to improve the light flux within the photodetectors is the use of plasmon resonance [9]. Under certain conditions, an interface between dielectric and a material with negative relative dielectric permittivity (for instance good metals like silver or gold) will maintain electromagnetic waves confined to the interface and evanescent (i.e. exponentially decaying) in both directions from the interface surface. Such waves are termed surface plasmons polaritons (SPP). Plasmon waves may propagate along a planar guide, or be localized e.g. on the surface of nanoparticles (localized SPP). In each of these situations they ensure extremely large concentrations of electromagnetic field. Owing to this, they are very convenient for the enhancement of the operation of photodetectors generally, if the region of the concentrated field coincides with the active region of the photodetector. Obviously, this is especially useful for very thin detectors. Some methods for plasmonic enhancement that could be further modified for military grade detectors of reflected laser beam were originally proposed for photovoltaic solar cells [10] to [13]. The main problem with the use of plasmonic enhancement for infrared detector is that plasma resonance frequency at which the evanescent wave reaches its peak for metals is in the ultraviolet or visible part of the spectrum [14]. Thus, it is necessary to redshift the plasma frequency towards longer operating wavelengths. Several strategies were proposed to overcome this. One of them is to form complex patterns on detector surface which may serve as nanoaperture arrays [15] and [16] and which support the existence of the so-called designer ("spoof') plasmons [17]. In this way, the operating wavelength can be tailored to be proportional to the aperture dimensions and the spacing between them. Wavelengths 7 to 8 mm were obtained in this manner [16]. Another redshifting strategy was to immerse metal nanoparticles into a higher refractive index material, which resulted in shifting the characteristics from the visible part of the spectrum to the wavelengths of up to 1.5 mm [9]. Nanoparticles with sandwich structures were also utilized [16] where e.g. non-plasmonic material is covered by a thin shell of plasmonic material or there are several alternating layers of plasmonic and dielectric materials. Finally, one may use alternative low-loss plasmonic materials with intrinsically redshifted plasma frequency, like those described in [18]. In this work we consider possible novel strategies to further improve infrared detection in semiconductor detectors utilizing plasmonics. We consider the replacement of metal nanoparticles by transparent conductive oxides like tin oxide, indium oxide and zinc oxide. We also investigate the possibility to combine these materials with higher-index surrounding dielectric media and with additional patterning to obtain plasmonic scatterers enhancing the performance of thin-film infrared detectors. 2 TECHNOLOGICAL MECHANISM OF LIGHT TRAPPING USING PLASMONIC NANOPARTICLES In this section, we briefly outline the possibility to enhance the quantum efficiency (the number of photocarriers generated by a single incident photon) and specific detectivity of a photodetector (regardless of its wavelength range) when there is only a micrometer-thin active area. To this purpose we consider a typical composition profile of an Hg1-xCdxTe photodetector, as defined by its cadmium molar fraction x. An experimental dependence of x on the distance from the detector surface is shown in Fig. 1a. The profile was experimentally determined from an ISOVPE-produced detector by IR transmission measurement because the cut-off wavelength of an MCT detector is defined by the lowest value of x, which is the one near the detector surface (left part of Fig. 1a). In several successive steps a submicrometer-thin layer was removed from the detector surface utilizing chemical etching and for each thus obtained remaining structure its cut-off was again determined by IR transmission measurement, while the thickness of the remaining structure was measured utilizing a profilometer. 32 4 (m + ir) (1) where mp is the plasma frequency, r denotes damping factor describing losses (i.e. defines the imaginary part of the complex dielectric permittivity), while sx is the asymptotic relative dielectric permittivity. The plasma frequency is determined by the properties of free carriers in material as: * = * m sr. (2) a = 3V- (5) - + 2 Here enp is the complex and wavelength-dispersive relative dielectric permittivity of the plasmonic nanoparticles, defined by Eq. (1), sd is the permittivity of the surrounding dielectric medium and V is the geometrical volume of the nanoparticle. The plasmon resonance and the maximum scattering cross-section are achieved at snp = -2sd. The absorption cross-section is determined as: Cabs = Im (a). (6) It is important to note that losses within TCO nanoparticles are smaller than those in metals. At the same time, the plasmon resonance wavelength in such nanoparticles is shifted into the infrared part of the spectrum. The particular value of the resonant wavelength can be tailored by doping of TCO. Both facts are very important for the enhancement of the performance of the infrared semiconductor detectors 4 n A i: np £ d £ np £ d 2 ne where n is electron concentration, e is the free electron charge (1.6 10-19 C), s0 is the free space (vacuum) permittivity (8.854 10-12 F/m), and m* is the electron effective mass. The damping factor can be calculated from the material scattering data as: e r=-*, (3) Hm where fi is mobility of free carriers in TCO. The scattering cross-section of a particle is greatly enhanced by plasma resonance and may reach 4 REDSHIFTING STRATEGIES FOR TCO NANOPARTICLES In this section the properties of some possible photodetector enhancement configurations utilizing transparent conductive oxide nanoparticles or full oxide layers are assessed. A situation where plasmonic nanoparticles are deposited directly to the surface of the detector, i.e. the configuration shown in Fig. 2c is considered. An additional antireflection coating can be located over the plasmonic layer. We analyzed two different TCO nanoparticle materials, tin oxide (TO) and aluminum-doped zinc oxide (AZO). The TO nanoparticles are fabricated 371 utilizing a non-aqueous approach in autoclaves starting from a simple solution of SnCl4 in benzyl alcohol, while AZO is produced in pressurized reaction vessels in a microwave system. The nanoparticles size and morphology were characterized by scanning electron microscopy (SEM). Details on the fabrication and characterization procedures of these materials are out of the scope of this paper and can be found in [24] to [26]. 90 150 180 210 n = 1.8 270 330 Air, n = 1 Fig. 4. Angular distribution of radiation scattered from an AZO nanoparticle located at an interface between air (refractive index n = 1) and a substrate with n = 1.8 Based on the measured and calculated optical and plasmonic properties of these nanoparticles, we performed numerical simulation of the IR radiation scattering on them. In accordance with the experimental data quoted in [24] to [26] we considered a spherical dipole TCO nanoparticle with a radius 35 nm, located at an interface between a semi-infinite medium with a refractive index value n = 1 and a layer with n = 1.8. In our simulation the beam was assumed to arrive perpendicularly to the detector surface at a wavelength of 1.4 mm (near infrared). For our calculation we utilized Eqs. (3) to (8) and applied the approach to scattering cross section determination as outlined in [27]. Fig. 4 shows a large enhancement of scattering cross section, together with preferential distribution of the incident power into the photodetector in the direction of the incident beam and with an appearance of sidelobes in the simulated distribution due to the total internal reflection (TIR) effect. Thus, plasmonic nanoparticles made from alternative redshifted materials can be used for the enhancement of photodetector operation in the infrared wavelength range. The presented case corresponds to the situation shown in Fig. 3 a, and the active region is located on the left from the nanoparticle. It should be emphasized here that the radial distribution shown in Fig. 4 is related with a single plasmonic nanoparticle only (its dimensions and properties being defined above) and does not directly reflect the overall photodetector element performance which is further defined by the specific detectivity enhancement. A further redshifting strategy for plasmonic nanoparticles is to embed them into a medium with a value of refractive index higher than that of the nanoparticle [28]. The influence of the embedding medium with a higher value of dielectric permittivity was numerically assessed utilizing a simplified scattering model from [29]. The dielectric permittivity of the nanoparticle was determined using the simple mixmg m°de^ (stotal = [eparticle + emedlum]/2). The normalized cross-section is defined here in the usual manner as the ratio of the power scattered by a particle versus the total power intercepted by it. The simulated results shown in Fig. 5 show that an increase of the dielectric permittivity of the surrounding medium shifts the cross-section maximum towards longer infrared wavelengths. A very similar effect had previously been reported for metal plasmonic nanoparticles at shorter wavelengths [28]. "> 0.8