CN115000207A - 4H-SiC narrowband ultraviolet photoelectric detector - Google Patents
4H-SiC narrowband ultraviolet photoelectric detector Download PDFInfo
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- 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
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- 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 at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
- H01L31/1812—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System including only AIVBIV alloys, e.g. SiGe
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Abstract
The invention belongs to the technical field of ultraviolet photoelectric detection, and particularly relates to a 4H-SiC narrow-band ultraviolet photoelectric detector which comprises a top electrode layer, a semiconductor layer and a bottom electrode layer which are sequentially arranged from top to bottom, wherein the semiconductor layer is a 4H-SiC substrate, and the top electrode layer is a semitransparent metal electrode made of TiN; the bottom electrode layer is an opaque metal electrode. The invention utilizes the photoconduction difference generated by the device under the irradiation of light with different wavelengths to realize the 15nm narrow-band ultraviolet response performance, and the bright-dark current ratio and the responsivity of the device are superior to those of the detector in the prior art.
Description
Technical Field
The invention belongs to the technical field of ultraviolet photoelectric detection, and particularly relates to a 4H-SiC narrow-band ultraviolet photoelectric detector.
Background
The silicon carbide (SiC) ultraviolet detector has wide application in the fields of ultraviolet radiation dose measurement, fire early warning, sunlight radiation index measurement and the like. The SiC substrate material supplied on the market comprises two crystal forms of 4H-SiC and 6H-SiC. Among them, 4H-SiC has higher carrier mobility than 6H-SiC, and is more advantageous in the development of optoelectronic devices. Ultraviolet photodetectors based on 4H-SiC substrates have been extensively studied over the last two decades. All 4H-SiC photodetectors reported include PN or PIN diode type, metal-semiconductor-metal type, and the like. The PN or PIN diode type 4H-SiC ultraviolet photoelectric detector with the vertical structure has high external quantum efficiency, and can detect single photon when working in an avalanche mode, but main functional layers of P type 4H-SiC, N type 4H-SiC and the like in the devices need to be processed by an epitaxial method, the manufacturing process is complex, and the device cost is high. Compared with the metal-semiconductor-metal type 4H-SiC ultraviolet photoelectric detector with a simpler structure, the metal-semiconductor-metal type 4H-SiC ultraviolet photoelectric detector has lower manufacturing cost, and is expected to promote the ultraviolet photoelectric detector to be more widely and deeply applied in the fields of mobile phones, smart homes, wearable electronic products and the like.
The simplest metal-semiconductor-metal type 4H-SiC photoelectric detector is obtained by directly manufacturing a metal interdigital counter electrode on one side of the surface of 4H-SiC, and can be called as a horizontal metal-semiconductor-metal type 4H-SiC photoelectric detector. Most of reported horizontal metal-semiconductor-metal type 4H-SiC photodetectors firstly extend a P-type or N-type 4H-SiC film on a SiC substrate and then manufacture electrodes, and the additionally introduced extension process causes the great increase of the device cost. 2012, sweden
The Ni/Au interdigital electrode is directly processed on a 4H-SiC substrate by a photoetching method by the people, and horizontal metal is preparedSiC photodetectors of the semiconductor-metal type (literature: Physica Status Solidi (c)2012,9, 1680). Under a bias of-4V, the dark current of the device is 100fA, and the dark current is 500 muW/cm at a wavelength of 365nm 2 Under the irradiation of light, the bright current of the device is 10nA, and the ratio of bright current to dark current reaches 10 5 . In addition, the response of the device in an ultraviolet band has no wavelength selectivity, the response spectrum is wide, and the corresponding full width at half maximum is about 75 nm.
After investigation, no report is found on directly manufacturing a photoelectric detector with a vertical structure form on a semi-insulating 4H-SiC substrate. In addition, the reported 4H-SiC ultraviolet photoelectric detector has wide response bandwidth and no wavelength selection function. Vertical structure photodetectors also have the advantage of: the electrodes at the two ends can be respectively specially designed, so that higher flexibility is improved for the performance improvement of the device; the area array device can be manufactured by simple crossing of the transverse and longitudinal electrodes. Therefore, the vertical metal-semiconductor-metal type 4H-SiC narrow-band ultraviolet photoelectric detector with low cost and high performance has great significance.
Disclosure of Invention
The invention overcomes the defects of the prior art, and solves the technical problems that: A4H-SiC narrow-band ultraviolet photodetector with a high bright-dark current ratio is provided to obtain narrow-band response ultraviolet photoelectric detection performance with the high bright-dark current ratio.
In order to solve the technical problems, the invention adopts the technical scheme that: A4H-SiC narrow-band ultraviolet photoelectric detector comprises a top electrode layer, a semiconductor layer and a bottom electrode layer which are sequentially arranged from top to bottom, wherein the semiconductor layer is a 4H-SiC substrate, and the top electrode layer is a semitransparent metal electrode made of TiN; the bottom electrode layer is an opaque metal electrode.
The bottom electrode layer is an opaque metal electrode made of TiN or Al.
The thickness of the semiconductor layer is 500 micrometers +/-400 micrometers, the thickness of the top electrode layer is 15nm +/-5 nm, and the thickness of the bottom electrode layer is 200nm +/-100 nm.
The 4H-SiC substrate adopted by the semiconductor layer is of a semi-insulating type, and the resistivity of the 4H-SiC substrate is between 1e13ohm cm and 1e15ohm cm.
The resistivity of the 4H-SiC substrate used for the semiconductor layer is between 5e13ohm cm and 5e14ohm cm.
The preparation method of the 4H-SiC narrow-band ultraviolet photodetector comprises the following steps:
s1, cleaning the 4H-SiC substrate;
s2, manufacturing a top electrode on one side of the cleaned 4H-SiC substrate by using a magnetron sputtering method;
and S3, turning the sample by using a magnetron sputtering method on the basis of the manufactured device of the semitransparent top electrode, and manufacturing a bottom electrode on the other side of the 4H-SiC.
The cleaning of the 4H-SiC substrate comprises the following steps:
s101, using a measuring cylinder to enable hydrogen peroxide, ammonia water and deionized water to be mixed in a ratio of 10: 10: 1, then putting the 4H-SiC substrate into a polytetrafluoroethylene beaker, covering the opening of the beaker with aluminum foil paper, soaking for more than 20min, then taking out the 4H-SiC substrate, washing with clear water, and removing residual solution;
s102, adding deionized water into another polytetrafluoroethylene beaker, and adding the mixture into the beaker in a ratio of 4: 1 volume ratio of diluted nitric acid solution, putting the 4H-SiC substrate into the nitric acid solution, covering the opening of the beaker with aluminum foil paper, performing ultrasonic treatment for 30min, taking out the 4H-SiC substrate, washing the substrate with clear water, and removing residual solution;
s103, coating detergent on the surface of the slice, repeatedly rubbing and cleaning the 4H-SiC substrate under water flow until the 4H-SiC substrate is washed by clean water, and forming a uniform water film on the surface of the 4H-SiC substrate.
S104, vertically placing the 4H-SiC substrate on a beaker frame, placing the beaker frame in a glass beaker, and sequentially adding deionized water, acetone and an absolute ethyl alcohol solvent for ultrasonic treatment for 15 min; and after the 4H-SiC substrate is cleaned, putting the cleaned 4H-SiC substrate into a beaker filled with an isopropanol solvent for standby.
The manufacture of the top electrode comprises the following steps:
s201, mounting a top electrode target on a target head of a magnetron sputtering coating machine;
s202, attaching a loading metal mask plate to one side of the 4H-SiC substrate; then, loading the sample tray on a sample tray of a magnetron sputtering coating machine, wherein a metal mask plate is downward, and adjusting the sample tray to enable a 4H-SiC substrate to be positioned right above a target material;
s203, closing the magnetron sputtering cabin door, opening and zeroing a vacuum gauge, opening a mechanical pump and a pre-pumping valve on a display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening a gate valve and a molecular pump, and enabling the pressure of the cabin body to reach 10 DEG C -4 When Pa, opening an argon ionization valve and an argon channel power supply;
s204, sequentially opening an argon magnetic control valve, a mechanical valve and a flowmeter, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa;
s205, turning on a sputtering power supply, adjusting the power required by sputtering, after glow starting, further adjusting the pressure through a gate valve to ensure that the sputtering rate meets the film forming requirement, carrying out pre-sputtering for 10 minutes, then carrying out formal sputtering until the required film thickness is reached, taking out a sample from a film coating chamber, and unloading the metal mask.
The manufacturing of the bottom electrode comprises the following steps:
s301, mounting the bottom electrode target on a target head of a magnetron sputtering coating machine;
s302, turning over the top electrode plated sample, attaching a metal mask plate to the other side of the 4H-SiC substrate, loading the 4H-SiC substrate loaded with the metal mask plate on a sample holder of a magnetron sputtering film plating machine, enabling the metal mask plate to face downwards, and adjusting a sample tray to enable the 4H-SiC substrate to be located right above a target material;
s303, closing the magnetron sputtering cabin door, opening and zeroing the vacuum gauge, opening the mechanical pump and the pre-pumping valve on the display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening the gate valve and the molecular pump, and enabling the pressure of the cabin body to reach 10 DEG C -4 When Pa, opening an argon ionization valve and an argon channel power supply;
s304, sequentially opening an argon magnetic control valve, a mechanical valve and a flowmeter, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa;
s305, turning on a sputtering power supply, adjusting the power required by sputtering, further adjusting the pressure through a gate valve after starting, and pre-sputtering for 10 minutes; and finally, performing formal sputtering until the required film thickness is reached, taking out the sample from the film coating chamber, unloading the metal mask plate, and collecting the sample.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a 4H-SiC narrow-band ultraviolet photodetector which has a metal-4H-SiC-metal type vertical structure, a semi-transparent metal top electrode made of TiN is prepared on one side of a semi-insulating type 4H-SiC substrate, an opaque metal bottom electrode is prepared on the other side of the semi-insulating type 4H-SiC substrate, 20V forward bias or reverse bias is applied under illumination to achieve narrow-band response characteristics, a response peak value is positioned on the band edge absorbed by 4H-SiC, namely near the wavelength of 360nm, the full width at half maximum is about 15nm, and the 15nm narrow-band ultraviolet response performance is achieved by utilizing the photoconductive difference generated by devices under the illumination of different wavelengths of light.
2. The detector prepared by the invention has a structure of 10 5 High bright to dark current ratio of (A) and as low as pA/cm 2 A horizontally very low dark current density. This is because the intrinsic carrier concentration of the semi-insulating 4H — SiC is extremely low. On the other hand, the energy level of the semi-insulating 4H-SiC is a Fermi level clamped by a surface state, the height of a potential barrier formed after the metal is contacted with the semi-insulating 4H-SiC is irrelevant to the work function of the metal, and the potential barrier during the injection of the carriers is far higher than the energy of the thermally excited carriers, so that the injection of the carriers in an external circuit is effectively inhibited. The device has a peak wavelength of 360nm and an optical power density of 26.37 μ W/cm 2 When the current ratio reaches 10 5 The above.
3. The 4H-SiC narrow-band ultraviolet photoelectric detector provided by the invention has higher responsivity than the detector in the prior art.
Drawings
Fig. 1 is a schematic structural diagram of a 4H-SiC narrowband ultraviolet photodetector with a high bright-to-dark current ratio according to an embodiment of the present invention; in the figure: 1-a semiconductor layer, 2-a top electrode layer, 3-a bottom electrode layer;
fig. 2 is a current density-voltage characteristic curve of several vertical structure metal-semiconductor-metal type 4H-SiC narrowband ultraviolet photodetectors in a dark state according to an embodiment of the present invention; the device structure is TiN/4H-SiC/Al and TiN/4H-SiC/TiN respectively, the top electrode is 15nm thick, the 4H-SiC is 500 mu m thick, and the bottom electrode is 100nm thick;
fig. 3 is an energy band diagram of a vertical structure metal-semiconductor-metal type 4H-SiC narrowband ultraviolet photodetector provided in an embodiment of the present invention, where the semi-insulating type 4H-SiC is a fermi level clamped by a surface state, and a barrier height formed after a metal is contacted with the semi-insulating type 4H-SiC is independent of a metal work function;
FIG. 4 is a response spectrum (wavelength range 300nm-400nm) of a vertical structure metal-semiconductor-metal type 4H-SiC narrow band UV photodetector under 20V and-20V bias voltage provided by an embodiment of the present invention, wherein the top electrode is made of TiN with a thickness of 15nm, the 4H-SiC is 500 μm thick, and the bottom electrode is made of Al with a thickness of 100 nm;
fig. 5 is a schematic diagram of a working mechanism of a vertical structure metal-semiconductor-metal type 4H-SiC narrowband ultraviolet photodetector provided in an embodiment of the present invention; (a-b) is a schematic diagram of an electric field intensity distribution diagram and an operating mechanism of the device irradiated by 300nm light positioned in a Beer-Lambert waveband; (c-d) an electric field intensity distribution graph and an operating mechanism schematic diagram of the device irradiated by 360nm light in the resonant cavity wave band;
fig. 6 is a current density-voltage characteristic curve of several vertical structure metal-semiconductor-metal type 4H-SiC narrowband ultraviolet photodetectors in a bright state according to an embodiment of the present invention; the device structure is TiN/4H-SiC/Al and TiN/4H-SiC/TiN respectively, the top electrode is 15nm thick, the 4H-SiC is 500 mu m thick, and the bottom electrode is 100nm thick. The test light wavelength is 375nm, and the power density is 10.2mW/cm 2 ；
FIG. 7 is a current density-voltage characteristic curve of a reference Al/4H-SiC/Al vertical structure metal-semiconductor-metal type 4H-SiC in a bright state, with a top electrode thickness of 15nm, a 4H-SiC thickness of 500 μm, and a bottom electrode thickness of 100 nm. The test light wavelength is 375nm, and the power density is 10.2mW/cm 2 。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
As shown in fig. 1, an embodiment of the present invention provides a 4H-SiC ultraviolet photodetector having a vertical structure of a metal-semiconductor-metal type, specifically including a top electrode layer 2, a semiconductor layer 1 and a bottom electrode layer 3, where the semiconductor layer is a 4H-SiC substrate, and the top electrode layer is a semitransparent metal electrode made of TiN; the bottom electrode layer is an opaque metal electrode made of TiN or Al.
Specifically, in the present embodiment, the 4H — SiC substrate is a semi-insulating type, is a weak n-type, and has a resistivity of 1e13ohm cm to 1e15ohm cm.
Preferably, in the embodiment, the 4H-SiC substrate is semi-insulating type and weak n type, and the resistivity of the 4H-SiC substrate is between 5e13ohm cm and 5e14ohm cm.
Further, in this embodiment, the energy level of the semi-insulating 4H — SiC substrate is the fermi level clamped by the surface state, and the barrier height formed after the metal is in contact with the surface state is independent of the work function of the metal.
Further, in the embodiment, the thickness of the 4H-SiC substrate is 500 micrometers +/-400 micrometers, the thickness of the semitransparent top electrode layer is 15nm +/-5 nm, and the thickness of the bottom electrode layer is 100nm +/-50 nm.
Preferably, in the embodiment, the thickness of the 4H-SiC substrate is 500 μm +/-20 μm, the thickness of the semitransparent top electrode is 15nm +/-1 nm, and the thickness of the bottom electrode is 100nm +/-5 nm.
Example two
The second embodiment of the invention provides a preparation method of a 4H-SiC ultraviolet photoelectric detector, and the materials used in the second embodiment of the invention are as follows:
4H-SiC substrate, TiN target material, Al target material, hydrogen peroxide, ammonia water, deionized water, nitric acid, detergent, deionized water, acetone, absolute ethyl alcohol and metal mask. The combined dosage and screening criteria were as follows:
4H-SiC substrate: semi-insulating type, weak n type, with resistivity of 1e14ohm cm, 20mm × 20mm, thickness of 500 μm;
TiN target material: solid, copper backplane bound, 99.9% purity;
al target material: solid, 99.999% purity;
hydrogen peroxide: H2O2, 3%;
ammonia water: NH4OH, 25%
Deionized water: H2O 8000mL +/-50 mL;
nitric acid: HNO3, 68%
A liquid detergent: 2 plus or minus 0.5 mL;
acetone: CH3COCH3250 mL +/-5 mL;
anhydrous ethanol: 500mL plus or minus 5mL of C2H5OH 500;
metal mask plate: stainless steel; the strip-shaped patterns are 2mm in hollowed-out width and 5mm in spacing.
The preparation method of the 4H-SiC ultraviolet photodetector provided by the embodiment specifically includes the following steps:
and S1, cleaning the 4H-SiC substrate.
In step S1, the method for cleaning the 4H-SiC substrate includes:
s101, using a measuring cylinder to enable hydrogen peroxide, ammonia water and deionized water to be mixed in a proportion of 10: 10: 1, then putting the 4H-SiC substrate into a polytetrafluoroethylene beaker, covering the opening of the beaker with aluminum foil paper, soaking for more than 20min, then taking out the 4H-SiC substrate, washing with clear water, and removing residual solution;
s102, adding deionized water into another polytetrafluoroethylene beaker, and adding the mixture into the beaker in a ratio of 4: 1 volume ratio of diluted nitric acid solution, putting the 4H-SiC substrate into the nitric acid solution, covering the opening of the beaker with aluminum foil paper, performing ultrasonic treatment for 30min, taking out the 4H-SiC substrate, washing the substrate with clear water, and removing residual solution;
s103, coating detergent on the surface of the slice, repeatedly rubbing and cleaning the 4H-SiC substrate under water flow until the 4H-SiC substrate is washed by clean water, and forming a uniform water film on the surface of the 4H-SiC substrate.
S104, vertically placing the 4H-SiC substrate on a beaker frame, placing the beaker frame in a glass beaker, and sequentially adding deionized water, acetone and absolute ethyl alcohol solvent for 15min of ultrasound respectively. And after the 4H-SiC substrate is cleaned, putting the cleaned 4H-SiC substrate into a beaker filled with an isopropanol solvent for later use.
And S2, manufacturing a semitransparent top electrode on one side of the silicon surface of the cleaned 4H-SiC substrate by using a magnetron sputtering method.
In step S2, the method for manufacturing the translucent top electrode includes:
s201, mounting the TiN target on a target head of a magnetron sputtering coating machine.
S202, attaching a loaded metal mask plate to one side of the 4H-SiC substrate, loading the metal mask plate on a sample tray of a magnetron sputtering coating machine, enabling the metal mask plate to face downwards, and adjusting the sample tray to enable the 4H-SiC substrate to be located right above the TiN target.
S203, closing the magnetron sputtering cabin door, opening and zeroing a vacuum gauge, opening a mechanical pump and a pre-pumping valve on a display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening a gate valve and a molecular pump, and opening an argon ionization valve and an argon channel power supply when the cabin pressure reaches 10-4 Pa.
S204, opening an argon magnetic control valve, a mechanical valve and a flowmeter in sequence, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa.
S205, turning on a sputtering power supply, adjusting the power required by sputtering, and after glow starting, further adjusting the pressure through a gate valve to enable the sputtering rate to meet the film forming requirement. The pre-sputtering is carried out for 10 minutes, and then the formal sputtering is carried out. When the required film thickness is reached, the large baffle is closed, then the radio frequency sputtering power supply is closed, the sample is taken out from the film coating chamber, and the metal mask is dismounted.
And S3, turning the sample over on the basis of the manufactured top electrode device by using a magnetron sputtering method, and manufacturing a light-tight bottom electrode on the other side of the carbon surface of the 4H-SiC.
S301, mounting the bottom electrode target on a direct current target of a magnetron sputtering coating machine.
S302, turning over the sample plated with the TiN film layer, attaching a loaded metal mask plate to the other side of the 4H-SiC substrate, paying attention to protect the prepared film layer, loading the 4H-SiC substrate loaded with the metal mask plate on a sample support of a magnetron sputtering film plating machine, enabling the growth surface of the film to face downwards, and adjusting the sample support to enable the 4H-SiC substrate to be located right above the Al target.
S303, closing the magnetron sputtering cabin door, opening and zeroing a vacuum gauge, opening a mechanical pump and a pre-pumping valve on a display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening a gate valve and a molecular pump, and opening an argon ionization valve and an argon channel power supply when the cabin pressure reaches 10-4 Pa.
S304, opening an argon magnetic control valve, a mechanical valve and a flowmeter in sequence, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa.
S305, turning on a direct-current sputtering power supply, adjusting the power required by sputtering, correspondingly depositing at a rate of 0.05nm/S, and pre-sputtering for 5 minutes. And finally, performing formal sputtering, closing the large baffle plate and then closing the direct-current sputtering power supply when the required film thickness (100nm +/-50 nm) is reached, taking out the sample from the film coating chamber, unloading the metal mask plate, and collecting the sample, namely the TiN/4H-SiC/Al vertical structure metal-semiconductor-metal type 4H-SiC ultraviolet photoelectric detector.
Detection, analysis and characterization: and detecting, analyzing and characterizing the performance of the prepared 4H-SiC ultraviolet photoelectric detector.
Measuring a current density-voltage curve of the device in a dark state by using an Aglient B1500 high-precision digital source meter; measuring the response spectrum of the 4H-SiC ultraviolet photoelectric detector by using a Zhuoli Han xenon lamp, a Zhuoli Han monochromator and an Aglient B1500; the current density-voltage curve of the 4H-SiC uv photodetector in the bright state was measured with a Thorlabs 375nm LED and an AglientB 1500.
And (4) conclusion: dark-state current density characteristics, bright-state response spectrum characteristics and bright current density characteristics of 4H-SiC ultraviolet photodetectors made of different bottom electrode materials are analyzed. FIG. 2 shows the dark current density characteristic curves of the 4H-SiC UV photodetector of the present invention, which have structures of TiN/4H-SiC/Al and TiN/4H-SiC/TiN, respectively. Wherein the top electrode is made of TiN and has a thickness of 15nm, and the 4H-SiC semiconductorThe thickness of the body layer is 500 μm, the material of the bottom electrode is TiN or Al, and the thickness is 100 nm. As can be seen from FIG. 2, the dark current density of the devices of both structures is as low as pA/cm under 20V bias 2 Horizontal; the reason for this is that, on the one hand, the semi-insulating 4H-SiC of the present invention has an extremely low intrinsic carrier concentration, a resistivity of between 1e13ohm cm and 1e15ohm cm, and accordingly, a dark current induced by intrinsic carriers is extremely low. By theoretical calculation, the thickness is 0.5mm, and the sectional area is 4mm 2 The dark current density induced by intrinsic carriers is in the range of 0.006pA/cm under 20V bias 2 (corresponding to a resistivity of 1e15ohm cm) to 0.625pA/cm 2 (corresponding resistivity of 1e13ohm cm). On the other hand, the energy level of the semi-insulating 4H-SiC is the fermi level clamped by the surface state, the height of the barrier formed after the metal contacts the semi-insulating 4H-SiC is independent of the work function of the metal, and the barrier during carrier injection is much higher than the energy of the thermally excited carrier (as shown in fig. 3), so that the injected carrier in the external circuit is effectively suppressed. It is noted that the dark current density of the detector shown in fig. 2 is slightly higher than the theoretical value of dark current density induced by intrinsic carriers, since surface charges also participate in conduction.
As shown in FIG. 4, the 4H-SiC ultraviolet photodetector provided by the invention achieves narrow-band response under 20V or-20V bias voltage, and the response peak is located at the band edge of 4H-SiC absorption, specifically near the wavelength of 360nm, and the full width at half maximum is about 15 nm. This feature is distinguished from the horizontal structure metal-semiconductor-metal type 4H-SiC ultraviolet photodetectors described in the background (literature: Physica Status solid (c)2012,9,1680), whose full width at half maximum of the response spectrum is 75nm, whereas the full width at half maximum of the response spectrum obtained in the present invention is one fifth of the full width at half maximum of the response spectrum given in this background. The reason for the narrow-band response of the present invention is the difference in photoconductivity of the device under illumination with light of different wavelengths.
In addition, the 4H-SiC ultraviolet photoelectric detector provided by the invention has the incident light power density of 26.37 muW/cm under the wavelength of 360nm 2 Corresponding bright current density of 3.4 × 10 5 pA/cm 2 The ratio of bright to dark current reaches 10 5 The aboveThe corresponding responsivity is 17 mA/W. The performance index is better than the related performance of a horizontal metal-semiconductor-metal type SiC photoelectric detector in the background technology (literature: Physica Status Solidi (c)2012,9,1680), and the bright-dark current ratio reaches 10 5 The required incident light power density with 365nm wavelength is about 500 mu W/cm 2 The responsivity is about 6mA/W, which is obviously lower than the corresponding performance index of the device.
Fig. 5 (a) and (b) show the distribution and operation of the electric field intensity of 300nm light in Beer-Lambert wavelength band on the device, respectively. Fig. 5 (c) and (d) show the distribution and operation of the electric field intensity of 360nm light in the resonant cavity band on the device. For the Beer-Lambert waveband with a high light absorption coefficient, the absorption of incident light mainly occurs in a region close to the semitransparent top electrode, a surface absorption behavior is presented, photo-generated carriers are generated only on the surface close to the top electrode, and the photoconductivity of the region is high. These surface carriers are redistributed in the 4H-SiC bulk by diffusion and drift motion, as shown in fig. 5 (b). As the thickness of the 4H-SiC is far greater than the carrier diffusion distance, the carrier concentration is gradually reduced in a region far away from the top electrode, the photoconductivity is in a descending trend, the total photoconductivity of the device is influenced, and the bright current of the device in the wave band is inhibited. In contrast, in the resonant cavity band (e.g., 360nm), the optical field exists throughout the entire 4H-SiC region between the top and bottom electrodes, as shown in FIG. 5 (c). Further, the photogenerated carriers excited by this band are distributed relatively uniformly in the 4H — SiC body, as shown in fig. 5 (d). Therefore, the resonant cavity band device as a whole has a larger photoconductivity than the Beer-Lambert band, and thus a higher photocurrent is generated. In addition, for long wavelength bands greater than 400nm, the bright current is extremely low since 4H — SiC does not absorb light. Therefore, the 4H-SiC ultraviolet photoelectric detector of the invention has narrow-band response. In order to obtain a narrow-band response, the thickness of the 4H-SiC substrate in the present invention must be sufficiently thick, at least above 100 μm.
FIG. 6 shows the bright current density characteristic curve of the 4H-SiC photodetector of the present invention, with a test wavelength of 375nm and optical powerThe density is 10.2mW/cm 2 Wherein the device specific structure is the same as that of fig. 2. As can be seen from fig. 6, when the bottom electrode is TiN or Al, the bright current density curves of the devices almost coincide. If the top electrode uses an Al electrode with poor light transmission, the bright current of the device is significantly reduced, and FIG. 7 shows that the Al/4H-SiC/Al device has a wavelength of 375nm (the optical power density is 10.2 mW/cm) 2 ) The thickness of the top electrode is 15nm, and the thickness of the bottom electrode is 100 nm. Comparing the data shown in fig. 6 and 7, it can be seen that the device with Al as the top electrode at 20V resulted in a decrease in the bright current to 1/6 when TiN was used as the top electrode.
In conclusion, the semitransparent top electrode and the opaque bottom electrode are respectively manufactured directly on the front side and the back side of the semi-insulating type 4H-SiC substrate, and finally the 4H-SiC narrow-band ultraviolet photoelectric detector with high brightness-dark current ratio is obtained. The realized SiC ultraviolet photoelectric detector has narrow-band response characteristics under ultraviolet illumination, extremely low dark current density and high bright-dark current ratio, and has bright application prospect in the fields of mobile phones, smart homes, wearable electronic products and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A4H-SiC narrow-band ultraviolet photoelectric detector is characterized by comprising a top electrode layer, a semiconductor layer and a bottom electrode layer which are sequentially arranged from top to bottom, wherein the semiconductor layer is a 4H-SiC substrate, and the top electrode layer is a semitransparent metal electrode made of TiN; the bottom electrode layer is an opaque metal electrode.
2. The 4H-SiC narrow band UV photodetector of claim 1, wherein the bottom electrode layer is an opaque metal electrode made of TiN or Al.
3. The 4H-SiC narrow band UV photodetector of claim 1, wherein the thickness of the semiconductor layer is 500 μm ± 400 μm, the thickness of the top electrode layer is 15nm ± 5nm, and the thickness of the bottom electrode layer is 200nm ± 100 nm.
4. The 4H-SiC narrow band UV photodetector of claim 1, wherein the 4H-SiC substrate used in the semiconductor layer is semi-insulating and has a resistivity of 1e13ohm cm to 1e15ohm cm.
5. The narrow band 4H-SiC UV photodetector of claim 4, wherein the semiconductor layer employs a 4H-SiC substrate having a resistivity of between 5e13ohm cm and 5e14ohm cm.
6. The method for preparing a 4H-SiC narrow-band ultraviolet photodetector as claimed in claim 1, comprising the following steps:
s1, cleaning the 4H-SiC substrate;
s2, manufacturing a top electrode on one side of the cleaned 4H-SiC substrate by using a magnetron sputtering method;
and S3, turning the sample by using a magnetron sputtering method on the basis of the manufactured device of the semitransparent top electrode, and manufacturing a bottom electrode on the other side of the 4H-SiC.
7. The method for manufacturing a 4H-SiC narrow band ultraviolet photodetector as claimed in claim 6, wherein the cleaning of the 4H-SiC substrate comprises the following steps:
s101, using a measuring cylinder to enable hydrogen peroxide, ammonia water and deionized water to be mixed in a proportion of 10: 10: 1, then putting the 4H-SiC substrate into a polytetrafluoroethylene beaker, covering the opening of the beaker with aluminum foil paper, soaking for more than 20min, then taking out the 4H-SiC substrate, washing with clear water, and removing residual solution;
s102, adding deionized water into another polytetrafluoroethylene beaker, and adding the mixture into the beaker in a ratio of 4: 1 volume ratio of diluted nitric acid solution, putting the 4H-SiC substrate into the nitric acid solution, covering the opening of the beaker with aluminum foil paper, performing ultrasonic treatment for 30min, taking out the 4H-SiC substrate, washing the substrate with clear water, and removing residual solution;
s103, coating detergent on the surface of the slice, repeatedly rubbing and cleaning the 4H-SiC substrate under water flow until the 4H-SiC substrate is washed by clean water, and forming a uniform water film on the surface of the 4H-SiC substrate.
S104, vertically placing the 4H-SiC substrate on a beaker frame, placing the beaker frame in a glass beaker, and sequentially adding deionized water, acetone and an absolute ethyl alcohol solvent for ultrasonic treatment for 15 min; and after the 4H-SiC substrate is cleaned, putting the cleaned 4H-SiC substrate into a beaker filled with an isopropanol solvent for standby.
8. The method for manufacturing a 4H-SiC narrow-band ultraviolet photodetector as claimed in claim 6, wherein the manufacturing of the top electrode comprises the following steps:
s201, mounting a top electrode target on a target head of a magnetron sputtering coating machine;
s202, attaching a loading metal mask plate to one side of the 4H-SiC substrate; then loading the sample on a sample tray of a magnetron sputtering coating machine, enabling a metal mask plate to face downwards, and adjusting the sample tray to enable a 4H-SiC substrate to be positioned right above the target material;
s203, closing the magnetron sputtering cabin door, opening and zeroing a vacuum gauge, opening a mechanical pump and a pre-pumping valve on a display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening a gate valve and a molecular pump, and enabling the pressure of the cabin body to reach 10 -4 When the pressure is Pa, opening an argon ionization valve and an argon channel power supply;
s204, sequentially opening an argon magnetic control valve, a mechanical valve and a flowmeter, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa;
s205, turning on a sputtering power supply, adjusting the power required by sputtering, after glow starting, further adjusting the pressure through a gate valve to ensure that the sputtering rate meets the film forming requirement, carrying out pre-sputtering for 10 minutes, then carrying out formal sputtering until the required film thickness is reached, taking out a sample from a film coating chamber, and unloading the metal mask.
9. The method for manufacturing a 4H-SiC narrow-band ultraviolet photodetector as claimed in claim 6, wherein the manufacturing of the bottom electrode comprises the following steps:
s301, mounting the bottom electrode target on a target head of a magnetron sputtering coating machine;
s302, turning over the top electrode plated sample, attaching a metal mask plate to the other side of the 4H-SiC substrate, loading the 4H-SiC substrate loaded with the metal mask plate on a sample holder of a magnetron sputtering film plating machine, enabling the metal mask plate to face downwards, and adjusting a sample tray to enable the 4H-SiC substrate to be located right above a target material;
s303, closing the magnetron sputtering cabin door, opening and zeroing a vacuum gauge, opening a mechanical pump and a pre-pumping valve on a display screen, closing the pre-pumping valve when the pressure is reduced to 30Pa, opening a gate valve and a molecular pump, and enabling the pressure of the cabin body to reach 10 DEG C -4 When Pa, opening an argon ionization valve and an argon channel power supply;
s304, sequentially opening an argon magnetic control valve, a mechanical valve and a flowmeter, selecting proper argon flow, and then adjusting a gate valve of the molecular pump to maintain the pressure of the cavity at 2 Pa;
s305, turning on a sputtering power supply, adjusting the power required by sputtering, further adjusting the pressure through a gate valve after starting, and pre-sputtering for 10 minutes; and finally, performing formal sputtering until the required film thickness is reached, taking out the sample from the film coating chamber, unloading the metal mask plate, and collecting the sample.
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| CN113013278A (en) * | 2021-03-12 | 2021-06-22 | 太原理工大学 | Silicon carbide-based full-spectrum response photoelectric detector and preparation method thereof |
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| Title |
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| E.DANIELSSON: "Thermal stability of sputtered tin as metal gate on 4H-SIC", 《MATERIALS SCIENCE FORUM》, vol. 264, pages 805 - 806 * |
| HSUEH-I CHEN: "Epitaxial growth of TiN on (0001) semi-insulating 4H-SiC substrate by reactive sputtering", 《SURFACE AND COATINGS TECHNOLOGY》, vol. 437, pages 1 - 5 * |
| 严贤雍: "基于表面等离激元效应的金属-半导体-金属型4H-SiC热电子光电探测器", 《中国硕士学位论文全文数据库（工程科技Ⅰ辑）》, no. 1, pages 25 - 26 * |
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