WO2022045913A1 - Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi - Google Patents

Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi Download PDF

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Publication number
WO2022045913A1
WO2022045913A1 PCT/RS2020/000012 RS2020000012W WO2022045913A1 WO 2022045913 A1 WO2022045913 A1 WO 2022045913A1 RS 2020000012 W RS2020000012 W RS 2020000012W WO 2022045913 A1 WO2022045913 A1 WO 2022045913A1
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Prior art keywords
film
electrode
semiconductor
temperature
detector
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PCT/RS2020/000012
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English (en)
Inventor
Jovana STANOJEV
Jovan Matovic
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Institut Biosens - Istrazivacko Razvojni Institut Za Informacione Tehnologije Biosistema
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Priority to PCT/RS2020/000012 priority Critical patent/WO2022045913A1/fr
Priority to EP20788910.6A priority patent/EP4205183A1/fr
Publication of WO2022045913A1 publication Critical patent/WO2022045913A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/103—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN homojunction type
    • H01L31/1037—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN homojunction type the devices comprising active layers formed only by AIVBVI compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H01L31/02327—Optical elements or arrangements associated with the device the optical elements being integrated or being directly associated to the device, e.g. back reflectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
    • H01L31/0325—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te characterised by the doping material

Definitions

  • the present invention relates to photovoltaic detector of infrared radiation. In another aspect the invention relates to methods for fabrication such detectors.
  • the invention is classified to the field of semiconductor electrical engineering, i.e. to the primary class HO IL and the secondary class H01L 21/04, H01L 31/00, H01L 31/0272, H01L 31/103 and H01L 31/18.
  • the technical problem solved by described invention is fabrication of polycrystalline photovoltaic detector of infrared radiation sensitive in 1 - 5 pm range, which operates at room temperatures. Formation of P-N homojunction, the main structure of the described photovoltaic detectors in an IV - VI semiconductor class with narrow band-gap of ⁇ 0.3 eV at ambient temperatures in a technically simple and affordable manner is still an unsolved challenge.
  • Infrared detectors based on IV- VI lead compounds (lead selenide, lead sulfide, lead telluride) are known in the Art for a long time and described as an example in “METHOD OF PRODUCTION OF LEAD SELENIDE PHOTODETECTOR CELLS” U.S. Pat. 2,997.409, 1961 that discloses the photoconductive detector based on N - type lead selenide. Since then, the design and performance of the detectors have been improved evolutionarily, but successful devices essentially remain unchanged for decades.
  • P - type semiconductor poly crystalline film of IV- VI lead compound around 1 pm thick is deposited between two planar contact electrodes, preferably from gold, subsequently non-selective doped of the entire film with oxygen, or oxygen/halogen dopants, and thereby converts the P - type film into N - type semiconductor, which is sensitive to infrared radiation.
  • Performances of the detector which operates at ambient temperatures, are remarkably high for a photoconductive device sensitive in 1 - 5 pm wavelengths, due to a suppression of the Auger recombination mechanism in the polycrystalline film, although the exact mechanism of the suppression has not yet been fully elucidated.
  • the presented invention disclose a fabrication method of photovoltaic infrared detector by formation of P-N homojunction in P - type polycrystalline film consisting of the IV-VI semiconductor group, more specifically from lead compounds of sulphur, selen or tellurium (PbS, PbSe or PbTe), in the manner that only a layer in the cross-section of that film is converted to N - type semiconductor by precisely controlled heating of one surface of the film to reach a temperature range allowing dopants, oxygen, or mixture of oxygen and halogen elements, to diffuse into the film to predefined depth and concentration, while the portion of the film underneath does not change, i.e. remains P - type semiconductor.
  • PbS, PbSe or PbTe lead compounds of sulphur, selen or tellurium
  • the formed layer of the N-type semiconductor forms core-shell ⁇ .-structure, where the core of the grains remain P-type and the shell of the grains are converted into N-type, preserving the Auger recombination suppression centers, a crucial structure responsible for a high performance of contemporary photoconductive detectors from IV-VI compounds.
  • the exposed surface of the film is heated by irradiation using pulses of electromagnetic energy in range of ultraviolet, visible, or infrared radiation.
  • the wavelength of radiation, pulse duration, pulse frequency, process duration and specific pulse energy are selected in such way, that only thin semiconductor layer just below the irradiated surface reaches the temperature required for diffusion of the dopants in the film, which ranges from 300 to 600 °C.
  • This process in a simple and technically feasible way, forms a P-N barrier in the IV-VI semiconductor film and can be used to fabricate a photovoltaic infrared radiation detector.
  • the second aspect the present invention discloses the detector of infrared radiation consisting of polycrystalline lead sulfide, lead selenide, or lead telluride thin film, which comprises a P- N junction within the cross-section of the film, and the film situated between first nontransparent infrared and reflecting electrode attached to a substrate with proper mechanical and thermal expansion properties, and partially transparent second electrode atop.
  • Figure 1 shows the flow-chart of processes for fabrication of the photovoltaic infrared detector.
  • Figure 2 shows a deposited P-type semiconductor film composed of compound IV-VI, side view.
  • Figure 3 shows the temperature on the exposed surface of the film during irradiation of the film with a pulsed radiation source, results of the model.
  • Figure 4 shows the temperature gradient along the cross section of the film created during irradiation if the exposed surface of the film with a pulsed radiation source, results of the model.
  • Figure 5 shows a formed photovoltaic infrared detector with a P-N homojunction, side view.
  • Figure 6 shows schematically formation of P-N homojunction irradiated with a defocused laser beam.
  • Figure 7 shows the top view of the photovoltaic infrared detector with P-N homojunction.
  • Figure 8 shows the current- voltage curves of a photovoltaic detector in the dark and illuminated by infrared radiation.
  • the detector shown in Figure 5 consists of a substrate 200, a first contact electrode 201, which simultaneously serves as a mirror of incoming infrared radiation, a P-type semiconductor layer 500 of lead sulfide, lead selenide or lead telluride, connected to the N- type layer of that semiconductor 501 to form a P - N homojunction and second contact partially transparent electrode 502.
  • the process of making such a detector consists of steps according to Figure 1.
  • the first step in the fabrication process 100 is preparation of the substrate for deposition of the first electrode.
  • Non-conductive materials such as glass, ceramics, polymers and composite materials and like can be used for the substrate, as well as conductive materials, such as metals or alloys including silicon, copper, silver, gold, tungsten, tantalum, or various alloys.
  • the substrate 200 Prior to the electrode deposition, the substrate 200 is treated with a series of polar solvents, such as ethyl alcohol, isopropyl alcohol or acetone, deionized water, and finally treated in plasma, a common process in the Art.
  • polar solvents such as ethyl alcohol, isopropyl alcohol or acetone, deionized water
  • the next step is the deposition of the first electrode consisting of gold 201, purity of 98% to 99.99%, by physical or chemical deposition in a thickness range from 100 to 500 nm. Thicknesses over 500 nm do not improve performances of the device. If the substrate material, such as silicon, glass or polymer, has a poor adhesion to gold, a 10 nm thick adhesive layer, such as aluminum, titanium or chromium about may be applied to the substrate 200, which represents a common process in the Art, Figure 2.
  • the next step 102 is deposition of a 0.2 - 20 pm thick semiconductor film over the electrode 201, by physical deposition process, thermal vaporization, electron gun, sputtering, plasma deposition, or chemical deposition from a solution common in the Art.
  • Deposited semiconductor film 202 is a P-type polycrystalline film, regardless of the deposition method.
  • Figure 2 shows the structure of the detector after the film deposition. This structure consists of the substrate 200, the first electrode 201, and the semiconductor film 202.
  • the next step 103 is formation of P-N homojunction in the deposited film.
  • the exposed surface of the film 203 in Figure 2 is irradiated by short and strong pulses of electromagnetic radiation from ultraviolet, visible, or infrared radiation at wavelengths shorter than 5 pm. During the irradiation, the absorbed electromagnetic energy is converted into the thermal energy that heats up the exposed surface of the film 203 and the generated heat flows by conduction into the film below the exposed surface 203.
  • the semiconductor Since the semiconductor is nontransparent for wavelengths shorter than 5 pm, i.e. has a high absorption coefficient to the incoming radiation, the radiation is converted into the heat which is predominantly generated just below the exposed surface 203.
  • An important novelty of this process is that the parameters of the pulse source are setup to heat the surface 203 and the layer just below the surface to a temperature range from 300 to 600°C, which is required for controlled diffusion of the dopants into the top part of the film 202.
  • the second layer 204 of the film 202 Just underneath the top part, the second layer 204 of the film 202, remains at a temperature below the diffusion temperature, since it is thermally connected to the substrate 200 that has a thermal capacity 100 - 1000 times greater than the thermal capacity of the film.
  • Such mismatch of thermal capacities is sufficient to dissipate the heat generated on the surface 203, Figure 2.
  • the process can be adjusted to keep temperature of the surface 203 relatively constant in the range sufficient for dopant diffusion, Figure 3 (modeling results).
  • the temperature gradient is formed along the cross section of the semiconductor film 202.
  • Figure 4 shows the temperature profile across the film 202, obtained by modeling of the heat flow within the film, and described under "detector fabrication example”. Heating of the exposed surface 203 is performed in the atmosphere of dopant, oxygen or a mixture of oxygen and a halogen element, iodine or bromine.
  • the film layer 501 is converted into the N-type semiconductor, while the remaining part of the film 500, as thermally firmly connected to the substrate, does not reach the temperature required for dopant diffusion, i.e. remains the P-type semiconductor, thus forming a P-N homojunction in the film 202.
  • an additional heat sink for example a cooler, Peltier element, or forced fluid flow, could be installed during the detector fabrication.
  • the slope of the temperature gradient that determines the depth of the P-N homojunction, the width of the depleted region and the dopant concentration, can be adjusted by irradiation parameters: wavelength, pulse duration, pulse frequency, process duration, and the specific pulse energy. Additionally, the parameters of the P-N homojunction can be adjusted by selecting the thickness of the layer 202, thermal capacity and thermal conductivity of the substrate 200, as well as the heat dissipation methods in order to optimize the infrared detector performance, but the invention disclosed here is not limited by the selection of process parameters.
  • Disclosed photovoltaic detector consists of the semiconducting polycrystalline film 202 of the lead salt from IV - VI compounds, which in its cross-section contains a P-type semiconducting layer 500, N - type semiconducting layer 501 hence forming P - N junction in the polycrystalline material, and embedded between first gold collecting electrode 201, which also serves as a mirror for incoming infrared radiation which pass through the semiconducting film 202, and a partially transparent second collecting electrode 502.
  • the entire structure is situated on a substrate of conduction or non-conducting material with thermal expansion coefficient around 10" 5 /°C.
  • Silicon substrate 200 650 pm thick, was prepared by cleaning with ethanol, isopropyl, deionized water and treatment in plasma, in the manner customary in the Art.
  • the adhesion intermediate layer of titanium of 10 nm thickness was applied to the silicon substrate, and subsequently the gold electrode 201 was deposited by physical deposition at 200 nm thickness.
  • the surface of the semiconductor 203 was irradiated with defocused laser beam, Figure 6.
  • a Nd: YAG diode laser was used, which emits at wavelength of 1064 nm.
  • the laser beam emitted from the laser head 600 was directed by optical lens 601 adjusted in such a way that the focus of the laser beam was out of the exposed film surface 203, i.e. the focus of the laser beam focus was formed in the focal plane 604, Figure 6.
  • the area of irradiated surface of the semiconductor 203 had a diameter of about 2 mm 602, and the surface 203 was heated evenly ( Figure 3).
  • the laser beam energy was sufficient to heat the surface to the temperature required for oxygen diffusion into the layer underneath.
  • Figure 4 shows that the temperature on the surface 203 reached 450 °C, which was sufficient for diffusion of dopants into the film to a depth of 0.1 pm, while the remaining part of the film stayed under 350 °C, i.e no diffusion of dopant occurred (modeling results).
  • Pulsed radiation was emulated by moving the laser beam in the x - y direction with a wipe speed of 3 mm/s.
  • Other process parameters were: laser current 28 A, process duration between 10-15 min. In this process the P-N homojunction 0.1 pm beneath of the surface 203 was formed, Figure 4.
  • the second contact electrode, 502 in the form of a grid, was applied to the second surface of the formed N-type semiconductor 501, Figure 7.
  • Figure 8 shows the measured current-voltage dependence of the detector made in this way, which shows the presence of P-N homojunction in the structure.
  • Curve 1 in Figure 8 is a typical U/I characteristic of a diode
  • curve 2 represents the U/I dependence when the diode is irradiated with an infrared radiation source, which proves that a P-N compound is obtained in the structure and that the device is sensitive to infrared radiation.
  • Infrared detectors based on IV- VI semiconductors are the most widely used detectors for the range 1 - 5 pm due to their high sensitivity when working at room temperature and relatively low cost. These detectors are used in spectroscopy, food and gas analysis, as well as missile guidance. The new detector, described here, would find application in the same areas, but would have superior performance than current devices in terms of speed, sensitivity, specific detectivity (D*) and low operating voltage.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Light Receiving Elements (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un détecteur de rayonnement infrarouge photovoltaïque qui est fourni en formant une homojonction P-N dans le film (202) de semi-conducteur polycristallin IV-VI de type P en chauffant une surface (203) du film à une température à laquelle advient la diffusion de dopant, d'oxygène ou d'un mélange d'oxygène et d'élément halogène tandis que la surface opposée de ce film est maintenue à une température inférieure à la température requise pour la diffusion. De cette manière, dans la section transversale du film semi-conducteur, un gradient de température est formé, de telle sorte que la surface du film irradié et une couche au-dessous de celle-ci sont converties en une couche semi-conductrice de type N (501) tandis que la partie restante forme une couche semi-conductrice de type P (500). Le chauffage est effectué en irradiant la surface du semi-conducteur avec des impulsions d'énergie électromagnétique dans la région de rayonnement ultraviolet, visible ou infrarouge, moyennant quoi le rayonnement électromagnétique est converti en chaleur qui chauffe la surface (203) du semi-conducteur et la couche au-dessous de la surface à la température requise. Les paramètres de l'impulsion de rayonnement sont sélectionnés de telle sorte que seule une zone étroite au-dessous de la surface du semi-conducteur irradié atteint une température pour la diffusion de dopant qui est comprise entre 300 et 600 °C. Ainsi, une photodiode ayant une homojonction P-N dans la section transversale de film est fournie, laquelle est sensible au rayonnement infrarouge dans la plage de longueurs d'onde de 1 à 5 pm.
PCT/RS2020/000012 2020-08-27 2020-08-27 Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi WO2022045913A1 (fr)

Priority Applications (2)

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PCT/RS2020/000012 WO2022045913A1 (fr) 2020-08-27 2020-08-27 Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi
EP20788910.6A EP4205183A1 (fr) 2020-08-27 2020-08-27 Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi

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PCT/RS2020/000012 WO2022045913A1 (fr) 2020-08-27 2020-08-27 Détecteur de rayonnement infrarouge photovoltaïque à partir de semi-conducteurs polycristallins iv-vi

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2997409A (en) 1959-11-04 1961-08-22 Santa Barbara Res Ct Method of production of lead selenide photodetector cells
US9887309B2 (en) 2012-12-13 2018-02-06 The Board of Regents of the University of Okalahoma Photovoltaic lead-salt semiconductor detectors
WO2018193045A1 (fr) * 2017-04-20 2018-10-25 Trinamix Gmbh Détecteur optique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2997409A (en) 1959-11-04 1961-08-22 Santa Barbara Res Ct Method of production of lead selenide photodetector cells
US9887309B2 (en) 2012-12-13 2018-02-06 The Board of Regents of the University of Okalahoma Photovoltaic lead-salt semiconductor detectors
WO2018193045A1 (fr) * 2017-04-20 2018-10-25 Trinamix Gmbh Détecteur optique

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
AHMED RASIN ET AL: "Mid-infrared photoresponse of electrodeposited PbSe thin films by laser processing and sensitization", OPTICS AND LASERS IN ENGINEERING, vol. 134, 16 July 2020 (2020-07-16), AMSTERDAM, NL, pages 106299, XP055806364, ISSN: 0143-8166, DOI: 10.1016/j.optlaseng.2020.106299 *
KASIYAN VLADIMIR ET AL: "Infrared detectors based on semiconductor junction of PbSe", JOURNAL OF APPLIED PHYSICS, AMERICAN INSTITUTE OF PHYSICS, US, vol. 112, no. 8, 15 October 2012 (2012-10-15), pages 86101 - 86101, XP012167763, ISSN: 0021-8979, [retrieved on 20121017], DOI: 10.1063/1.4759011 *
MOON-HYUNG JANG ET AL: "Electrical transport properties of sensitized PbSe thin films for IR imaging sensors", SEMICONDUCTOR SCIENCE TECHNOLOGY, IOP PUBLISHING LTD, GB, vol. 34, no. 6, 21 May 2019 (2019-05-21), pages 65009, XP020334609, ISSN: 0268-1242, [retrieved on 20190521], DOI: 10.1088/1361-6641/AB19E7 *
REN Y.X. ET AL: "Fabrication of lead selenide thin film photodiode for near-infrared detection via O2-plasma treatment", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 753, 19 March 2018 (2018-03-19), CH, pages 6 - 10, XP055806362, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2018.03.227 *
SIMONDS BRIAN J ET AL: "Laser processing for thin film chalcogenide photovoltaics: a review and prospectus", JOURNAL OF PHOTONICS FOR ENERGY, SOCIETY OF PHOTO-OPTICAL INSTRUMENTATION ENGINEERS, 1000 20TH ST. BELLINGHAM WA 98225-6705 USA, vol. 5, no. 1, 19 January 2015 (2015-01-19), pages 50999, XP060053836, DOI: 10.1117/1.JPE.5.050999 *

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