Silicon-based photodetectors with expanded bandwidth
10403781 ยท 2019-09-03
Assignee
Inventors
Cpc classification
H01L27/15
ELECTRICITY
H01L31/1085
ELECTRICITY
Y02E10/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L31/07
ELECTRICITY
H01L31/02024
ELECTRICITY
International classification
H01L27/15
ELECTRICITY
H01L29/06
ELECTRICITY
H01L31/07
ELECTRICITY
Abstract
A hot carrier photodetector has been developed that absorbs approximately 80% of broadband infrared radiation by using a planar nanoscale back metal contact to silicon. Based on the principles of the hot carriers generation in ultrathin metal films, silicon-based CMOS image sensors are developed which operate in the IR diapason. The device uses absorption in an ultrathin metallic nanostructure to generate therein a non-equilibrium electron distribution which subsequently is injected into the silicon material via a Schottky contact at the Si body, thus generating a photoresponse to an incident IR radiation. A pixeled array including interconnected hot carriers metallic nanostructured cell(s) and traditional RGB elements is envisioned to enable RGB-IR imaging from a single silicon based wafer.
Claims
1. Si-based photodetecting system operating in a bandwidth expanded into Infrared (IR) diapason, comprising: at least one IR photodetecting cell manufactured with: a Si (silicon) substrate having a first surface and a second surface opposite to said first surface, wherein said silicon has a Si energy bandgap; a Schottky contact formed on said second surface of said Si substrate, said Schottky contact including a thin conductive film having a nanometer scale thickness h and formed in substantially contiguous contact with said second surface of said Si substrate, thereby creating an energetic barrier having a height q.sub.B between said Si substrate and said thin conductive film; and an anti-reflection coating formed on said first surface of said Si substrate, and an ohmic contact formed on at least a portion of said first surface of said Si substrate; wherein, upon illumination of said first surface of said Si substrate with a radiation having an in air wavelength .sub.0 and having photons energy below said Si energy bandgap, said radiation passes through said Si substrate in a direction towards said second surface thereof, is absorbed in said thin conductive film of said Schottky contact, and excites hot carriers having an excitation energy exceeding said barrier height q.sub.B, and wherein said hot carriers are injected in said Si substrate through said barrier, thus creating a photoresponse to said incident radiation.
2. The Si-based photodetecting system of claim 1, further including at least first and second electrical connections, each coupled to a respective one of said ohmic contact and said thin conducting film, wherein said photoresponse is obtained between said first and second electrical connections.
3. The Si-based photodetecting system of claim 1, wherein said thin conducting film has a refractive index m=n+ik, wherein n>>0, and wherein n and k are real and imaginary parts of the refractive index m, respectively.
4. The Si-based photodetecting system of claim 1, wherein said thin conducting film is formed from a material including at least one of Pt, Fe, Cr, Ti, Cu, Al, Ni, Au, and alloys thereof.
5. The Si-based photodetecting system of claim 1, wherein said anti-reflection coating is formed from a dielectric material having a refractive index smaller than a refractive index of Si.
6. The Si-based photodetecting system of claim 1, wherein said thickness h of said thin film is shorter than said wavelength .sub.0 of said incident radiation, h<<.sub.0/2.
7. The Si-based photodetecting system of claim 1, wherein said thickness h of said thin conductive film falls in a nanometer range.
8. The Si-based phoodetecting system of claim 1, wherein the wavelength .sub.0 of the incident radiation falls in the IR diapason, said wavelength .sub.0 exceeding 1.1 m.
9. The Si-based photodetecting system of claim 1, wherein said Schottky contact barrier height q.sub.B is tuned to control said photoresponse.
10. The Si-based photodetecting system of claim 9, wherein said Schottky contact barrier height q.sub.B is reduced by heavily doping said Si substrate in proximity to said thin conductive film.
11. The Si-based photodetecting system of claim 9, wherein said Schottky contact barrier height q.sub.B is tuned by applying an external bias voltage thereto.
12. The Si-based photodetecting system of claim 1, wherein said Si substrate is an n-type Si.
13. The Si-based photodetecting system of claim 1, wherein said photodetecting system includes a Si-based Complementary Metal-Oxide-Semiconductor (CMOS) image sensor formed with at least one said IR photodetecting cell.
14. The Si-based photodetecting system of claim 13, wherein said Si-based CMOS image sensor includes a CMOS chip incorporating said at least one IR photodetecting cell and red-green-blue (RGB) elements operatively interconnected therebetween in a pixel array.
15. The Si-based photodetecting system of claim 1, wherein said at least one of said second surface of said Si substrate and said thin conducting film in said at least one IR photodetecting cell is patterned to form a periodical nanostructure, including at least one of conducting microwires, microcones, metallic grating, metallic nanodisk array, 3-D nanostructures, and combinations thereof, said periodical nanostructure including said thin conductive film.
16. The Si-based photodetecting system of claim 1, wherein said second surface of said Si substrate is substantially flat, and wherein said thin conductive film is an unpatterned film.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
(16) Production of metal excited electron-hole pairs which lead to photo generation has been observed in a Metal-Semiconductor hot plasmonic structure 10, shown in
(17) For absorption of the light 12 in the metal 14, an electron 16 in the Fermi gas absorbs a photon and is excited to a higher energy state. These excited hot electrons 16 leave an empty state in the Fermi gas, generating hot holes 18. The hot carriers 16, 18 travel within the metal 14 and are subjected to scattering that results in the carriers' relaxation and recombination.
(18) At Infrared (IR) and optical frequencies, the mean free path (MFP) of the electrons can be larger than the thickness 20 of the metal film 14 (which may fall in the range of 10 s of nm).
(19) A fraction of these carriers will reach the Schottky (metal-semiconductor) interface (barrier) 22 and are able to traverse the metal-semiconductor barrier 22 to arrive at the opposite side containing the semiconductor 24. Ultimately, these excited carriers 16 are collected and provide power to an external load 26, as shown in
(20) Referring to
(21) The theory of high absorption due to the 0.sup.th order FP mode in an ultrathin, homogeneous film sandwiched between two non-absorbing dielectrics has been previously developed. Hgglund, et al. (Maximized Optical Absorption in Ultrathin Films and Its Application to Plasmon-Based Two-Dimensional Photovoltaics, Nano Lett. 10, 3135-3141, 2010) derived the optimal material indices and device conditions for maximized absorption.
(22) From their derivation, a nanometer scale metal film can absorb >50% of all incident radiation under the following conditions: (i) The real (n) and imaginary () parts of the thin film's refractive index are large and approximately equal (i.e., n0 when the refractive index is m=n+i); (ii) The index of the top dielectric (n.sub.t) is greater than or equal to the bottom index (n.sub.b), and (iii) The optical path length in the film is significantly shorter than the wavelength of incident light, (i.e. h.sub.0/2, where h is the film thickness and .sub.0 is the wavelength in air.
(23) The maximum possible absorption in the thin film is not determined by the optical constants of the film or the film's thickness alone, but rather by the optical properties of the dielectrics above and below the film and can be determined by:
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(25) Therefore, if n.sub.1n.sub.b, it is possible to obtain near perfect absorption of light in films two orders of magnitude thinner than the excitation wavelength. In the case where the top dielectric is silicon and the bottom is air, the maximum possible absorption is 77.8%.
(26) The subject device geometry, and its simplicity, is shown in
(27) The anti-reflecting coating may be manufactured as a single film or as a multi-layer structure.
(28) Upon illumination by photon energy 44 below the bandgap of Si, light passes through the anti-reflecting coating 34 (which may be fabricated, for example, from SiN.sub.x, or other dielectric materials having anti-reflection properties and which are suitable for use in photodetectors) and the silicon substrate 32 to be absorbed within the back side metal film 41.
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(30) The absorption in the thin film contact 40 to the Si material 32 is analytically calculated using Fresnel equations for a single layer stack of Si/(m=n+i)/Air for varying thicknesses, h, of the back side metal film 41 at a wavelength of 1.2 m.
(31) As shown in
(32) It can be observed in
(33) For larger thicknesses of the back side metal film, the resonance condition can be met by many common materials. For example, at h=20 nm, platinum (Pt), iron (Fe), chromium (Cr), and titanium (Ti) prove to be good candidates due to their indices (n, ) positioned in the center of the resonance peak (as shown in
(34) Analytical calculations for these materials (Pt, Fe, Cr, Ti) with varying wavelength and thicknesses show broadband absorption above 70% for films as thin as 10 nm, as shown in
(35) The FP resonance is possible for these materials (Pt, Fe, Cr, Ti) as long as h.sub.0/2. Therefore, high absorption is maintained across a broadband of sub-bandgap wavelengths (for Si) because the metal film thicknesses are 100 times smaller than the sub-bandgap wavelengths (for Si). By comparing the absorption in each material (Pt, Fe, Cr, Ti), it has been observed that Pt maintains high absorption with the thinnest film.
(36) The absorption was measured in the four thin films (Pt, Fe, Cr, Ti) for thicknesses corresponding to their theoretical calculated maximum absorption (shown in
(37) Experimentally, each sample of the device 30 (shown in
(38) The back side metal film 41 was then deposited on the silicon surface 42 opposite to the SiNx coating 34 to form a back side Schottky contact 40, as depicted in
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(40) As shown in
(41) In agreement with Eq. 1, if the metal is illuminated directly from air, by reversing the sample orientation, the maximum absorption will be significantly reduced to 22%, with n.sub.t1 (air) and n.sub.b3.5 (Si), as shown in the inset in
(42) The sample fabricated with the Pt film achieves maximum absorption for smaller layer thickness than the other metals, thus indicating that the probability for internal photoemission in this sample is larger. Also, the Pt film has a thin, relatively stable native oxide, emboldening its chance for usage in the subject photodetector.
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(44) In order for the absorption in the metal film to generate current, the absorbed radiation must excite hot electrons to the energy levels above the Schottky barrier, to be able to inject the exited electrons into the silicon to be collected as photocurrent. As a result, the measured photoresponse attained the range between 10.sup.4 and 10.sup.6 A/W at wavelengths 1.2-1.5 m.
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(46) The device having Pt film of 15.6 nm thickness has 2-3 times higher photoresponse compared to the device having the Pt film of the thickness of the 35.9 nm because of its over 10% improvement in absorption, and greater probability of internal photoemission due to the shorter electron path length to the Schottky barrier.
(47) The performance of the subject hot carrier photodetector has also been compared with the photoresponse of commercial and Si photodetectors when illuminating bare silicon. The measured 10.sup.6-10.sup.8 A/W photoresponse of silicon is due to trap states. The hot carrier effect in the devices manufactured with Pt film on Si produces a 10.sup.2 increase in photocurrent.
(48) For illumination beyond 1.25 m, the subject hot carriers photodetector with the Pt film having the thickness of 15.6 nm demonstrates higher photoresponse than a commercial Si photodetector. This measurement confirms that thin film deposition of Pt is an effective and low-cost solution for extending the bandwidth of silicon photodetectors.
(49) To demonstrate this phenomenon, transmission images of a gold (Au) spiral on a quartz substrate (shown in
(50) As shown in
(51) The commercial Si detector, as shown in
(52) Due to the fact that the hot carrier Si detector was not optimized for the wavelengths at or above the bandgap of silicon, the commercial Si detector produces significantly greater photoresponse at the bandgap, as shown in
(53) While the hot carrier detector with the Pt film extends the bandwidth of silicon detectors, further modifications can improve its photoresponsivity. For example, reducing the barrier height (of the Schottky contact) through heavy doping at the interface between Si and Pt can result in both increased bandwidth of the photocurrent generated by electrons excited near the Fermi energy, as well as collection of photo-excited carriers from the d-band states.
(54) Enhancements could also be made by using metal alloys for the Schottky contact to tune the optical properties of materials for greater absorption in thinner material thicknesses and to adjust the barrier heights for an increased hot carrier collection.
(55) Hot carrier generation from sub-bandgap absorption in the metal contacts is a low cost solution to extend the bandwidth of semiconductor photodetectors and other photovoltaic devices. It has been shown that by selecting materials for the Schottky contact with approximately equal real and imaginary refractive indices, such as, for example, Pt planar contact to silicon, a nearly 80% absorption of broadband sub-bandgap light can be attained in a nanometer scale layer.
(56) The hot carrier IR photodetector 30 was fabricated by depositing 15.6 nm thick Pt film on a silicon wafer and 10.sup.4-10.sup.6 A/W photoresponse was attained for irradiation wavelengths of 1.2-1.5 m.
(57) Reducing the Schottky barrier height and tailoring the thin film optical properties through metal alloys improves the optical performance of the subject device. Simplicity of the geometry and fabrication process make the subject hot carrier phenomenon straightforward for incorporation into current commercial fabrication of silicon detectors.
(58) Fabrication of the Subject Si-Based IR Photodetectors for Optical Measurements
(59) A number of samples were fabricated on 368 m thick, double side polished, <100> n-type silicon wafers (1-10 cm).
(60) For absorption measurements, wafers were pre-cleaned in a piranha etch (3:1 sulfuric acid (H2SO4) and hydrogen peroxide (H.sub.2O.sub.2)) to remove all organic material, a buffered oxide etch (BOE) was conducted to remove the native oxide. Wafers were subsequently dried under an N.sub.2 stream.
(61) After the pre-cleaning procedure, an anti-reflection coating of 165 nm SiN.sub.x was deposited using an Oxford plasma enhanced chemical vapor deposition (PECVD) system, and the thin film absorbing metal contacts were deposited using an Angstrom E-Beam Evaporator at a deposition rate of 1 s.sup.1 at a pressure of 210.sup.6 Torr.
(62) Fabrication of the Subject Si-Based IR Photodetectors for Electrical Measurements
(63) Si wafers were cleaned using the same procedures as for optical measurements, and ohmic contacts were formed by depositing aluminum (Al) through a shadow mask in a thin strip pattern along the top surface of each device.
(64) Subsequently, annealing at 425 C. in a forming gas of 96% Ar and 4% H.sub.2 was performed.
(65) The SiN.sub.x anti-reflection coating was then deposited in the routine similar to the fabrication of the cell for absorption measurements through a shadow mask protecting the Al ohmic contact.
(66) Finally, after removing the native oxide from the back surface of Si wafer with BOE (Buffered Oxide Etch), the absorbing metal contacts were deposited in the same method as for the absorption measurements through a shadow mask allowing for multiple metal thicknesses to be deposited on the same device.
(67) Optical and Electrical Measurements
(68) Specific wavelengths were selected from a supercontinuum source using an acousto-optic tunable filter (AOTF). Absorption measurements were taken in a 6 inch integrating sphere with radiation at near-normal incidence of 12.
(69) Two Germanium-based (Ge) photodiodes were used to measure the light intensity inside the integrating sphere and to monitor power fluctuations of the incident beam's intensity. The signal from each Ge photodiode was measured using a lock-in amplifier.
(70) Photoresponse signals of each sample, i.e., the Si-based IR photodetector, were measured using a lock-in amplifier. The power incident on the sample was simultaneously monitored with a calibrated Ge photodiode.
(71) To determine the Schottky barrier height, IV curves were obtained, and the barrier height was determined by a fit to the experimental data.
(72) Transmission Mapping
(73) The maps depicted in
(74) Principles of photonics, plasmonics and hot carrier behavior have been used to develop a new image sensor technology based on resonant absorption in thin metal films and the subsequent hot electron injection into a CMOS sensor. The subject design, method of fabrication, and testing of a single pixel device has been performed which demonstrated the ability to detect IR illumination using a thin metal structure on a Si substrate. The subject principles will make ubiquitous CMOS imaging sensors found in everyday electronics to record images in red, blue, green, and IR. It will enable thermal imaging on cell phones and other devices with wide-reaching applications ranging from bio-medical (e.g. detecting physiological changes) to the detection of failure mechanisms in mechanical or electronic devices/structures, fire detection, etc. Thus, there would be significant potential for both societal and economic impact of the subject system.
(75) Optical design of metallic ultra-absorbers in the IR spectrum has been focused on the optical design (via numerical simulation) of absorbing metallic nanostructures (based on Au, Al, Cu, and Ni) on Si.
(76) Finite Difference Time Domain (FDTD) simulations have been used to design optical structures that allow for tailored absorption near the metal interface; and structural optimizations have been performed to tune absorption throughout the near-IR spectrum, as well as calculations of expected photo-injected current have been conducted in order to design optimized metallic nanostructures capable of either tunable narrowband and broadband absorption throughout the IR spectrum (1-2 m) using Al, Cu, and Ni. Absorption have been obtained with Au which exceeded 60% over the desired frequency range, as shown in
(77) Fabrication of metallic ultra-absorbers (hot carrier generation) has been focused on the fabrication of optical structures capable of absorbing light near the metal surface to generate hot carriers.
(78) Lithography (photo- and e-beam) may be used to pattern optical structures followed by dry etching to create nano structure super-absorbers.
(79) Wavelength and angle dependent absorption measurements have been conducted on the fabricated structures.
(80) The principles underlying the device 30 shown in
(81) Alternatively to the IR Si-based photodetector 30 shown in
(82) As the period of the nanostructure is increased, the absorption (which occurs in the metal film) is red-shifted by itself as shown in
(83) The patterning may be advantageous due to the fact that the narrowband operation can be tuned by changing the period (or width) of the nano-lines.
(84) The energetic carriers excited within the gold are injected into the Si material, and subsequently are detected. For photons with sufficiently low energy (>2 m), carrier injection can be aided by applying an applied external bias.
(85)
(86) An experimental test bed to measure the optoelectronic response of the subject Si based devices operating in the IR spectrum has been developed, and the optics was used that enabled detection of photo-injected carriers using visible light for IR illumination.
(87) The measurement data demonstrated hot carrier collection for a CMOS-compatible pixel element.
(88) Improvement strategies have been developed which include: (a) For low collection efficiency for hot carriers, larger bias to reduce barrier height can be applied; (b) Metals with different work functions can be used to enhance the probability of current flow; (c) To obviate poor metal-insulator/semiconductor interface quality, annealing conditions can be modified and alloyed metals can be considered; (d) Metal oxidation can be used to avoid introduction of interface defects (e.g., Al to Al.sub.2O.sub.3); (e) Atomic layer deposition can be used for conformal coatings.
(89) Metallic nanostructures capable of either tunable narrow-band or broadband absorption throughout the IR (1-2 m) spectrum using Au, Al, Cu, or Ni have been developed which demonstrated the absorption levels above 70% over the desired frequency range.
(90) The present cells 10, 30, 60 are contemplated for incorporation as cells (pixels) in the next-generation RGB-IR CMOS imaging sensors for wide dissemination.
(91) Referring to
(92) Although this invention has been described in connection with specific forms and embodiments thereof, it will be appreciated that various modifications other than those discussed above may be resorted to without departing from the spirit or scope of the invention as defined in the appended claims. For example, functionally equivalent elements may be substituted for those specifically shown and described, certain features may be used independently of other features, and in certain cases, particular locations of elements, steps, or processes may be reversed or interposed, all without departing from the spirit or scope of the invention as defined in the appended claims.