CN110164997B - High-performance infrared detector based on high-hole-mobility GaSb nanowire and preparation method thereof - Google Patents
High-performance infrared detector based on high-hole-mobility GaSb nanowire and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
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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
- H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L31/03042—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds characterised by the doping material
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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 at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a high-performance infrared detector based on a high-hole-mobility GaSb nanowire and a preparation method thereof, wherein a dual-temperature-zone gas phase method is adopted, metallic tin is selected as a catalyst and a light doping source, the controllable growth of the high-hole-mobility GaSb nanowire is realized, and the field-effect hole mobility of the high-hole-mobility GaSb nanowire exceeds 1000cm2V‑1s‑1. The high-performance GaSb nanowire infrared detector prepared by adopting the micro-nano processing technology comprises Si/SiO2The device comprises a substrate, a single GaSb nanowire and a metal electrode. The device has excellent photoelectric characteristics, and shows 10 percent for infrared light of 1550 nanometers4High responsivity of ampere/watt, ultrafast response time of 143.4 microseconds and 237.0 microseconds, strong process controllability, simple operation and low cost.
Description
Technical Field
The invention relates to a high-performance infrared detector based on a high-hole-mobility GaSb nanowire and a preparation method thereof, belonging to the field of semiconductor nano materials and devices.
Background
The semiconductor infrared detector has important application in national defense fields such as information, monitoring, investigation, accurate guidance, laser positioning and the like and civil fields such as agricultural monitoring, biomedical treatment, space remote sensing, machine vision and the like. The characteristic properties of the infrared detector include equivalent noise power or detectivity, responsivity, photocurrent gain, response time, and the like. The high responsivity requires high detector mobility, long free carrier life, high quantum efficiency and small thickness; fast response times require fast diffusion and drift speeds of the photogenerated carriers. Therefore, the mobility of the device is improved, so that the performance of the infrared detector is further improved. Currently, most infrared detectors are based on toxic HgCdTe materials, and the III-family antimonide semiconductors have narrow bandwidth and high carrier mobilityThe material has the advantages of mobility, moderate heat conduction coefficient and the like, and is considered to be one of the materials for replacing mercury cadmium telluride in the field of future high-performance infrared detectors. Meanwhile, the one-dimensional nanowire material receives more and more attention by virtue of the advantages of ultrahigh specific surface area, high light absorption capacity, high sensitivity and low power consumption. Wherein, the gallium antimonide (GaSb) nanowire has ultrahigh theoretical hole mobility (1000 cm)2V-1s-1) And narrow bandwidth (0.72eV), which has inherent advantages in the fabrication of high performance infrared detectors.
Although the diameter, the length, the growth direction, the crystallinity and the like of the GaSb nanowire are well controlled in the prior growth method, the field effect hole mobility reaches 330-2V-1s-1But still far below high-performance electronic-type semiconductor materials, which directly leads to the bottleneck in the development of GaSb nanowire-based optoelectronic devices. Therefore, the method has important significance for obtaining GaSb nanowires with higher mobility and realizing high-performance photoelectronic devices. In an intrinsic cavity type (p-type) semiconductor, light doping can effectively improve the crystal quality and reduce the coulomb scattering effect, which is beneficial to improving the cavity mobility. On the other hand, in the method for synthesizing the nanowire by chemical vapor deposition, the used metal catalyst can be proved to be doped into the nanowire lattice in a trace amount, and the energy band structure and the electrical transport property of the nanowire can be regulated and controlled. Therefore, selecting a suitable metal catalyst compatible with the existing silicon process and realizing the light doping of the nanowire to regulate the mobility and the energy band structure of the nanowire is a difficult point faced by the current GaSb nanowire research. Therefore, the method for optimizing the growth of the GaSb nanowires has important significance for further improving the infrared detection performance of the GaSb nanowires.
The present invention has been made based on the above-mentioned current state of research.
Disclosure of Invention
Aiming at the problem of low hole mobility of the existing GaSb nanowire and the defect that most of the existing infrared detectors are based on toxic mercury cadmium telluride materials, the invention provides a synthesis method of the GaSb nanowire with high hole mobility, a high-performance infrared detector based on the GaSb nanowire and a preparation method of the high-performance infrared detector. The inventionBy adopting a surfactant assisted chemical vapor deposition method and selecting metallic tin as a catalyst and a light doping source for growing the GaSb nanowire, the high-mobility GaSb nanowire with uniform density and smooth surface is prepared, and the field effect hole mobility of the GaSb nanowire exceeds 1000cm2V-1s-1. Furthermore, the grown GaSb nanowire with high hole mobility is used for preparing the nanowire infrared detection device with high responsivity and high response speed, and the nanowire infrared detection device is simple to operate and low in cost.
The technical scheme of the invention is as follows:
a semiconductor device based on GaSb nanowire with high hole mobility comprises p-type silicon as a bottom gate electrode and Si/SiO2And a channel formed by GaSb nanowire materials is arranged between the source electrode and the drain electrode on the substrate, and the GaSb nanowire is doped with tin.
According to the invention, the diameter of the GaSb nanowire is preferably 30-50 nanometers, the length of the GaSb nanowire is more than or equal to 10 micrometers, and the surface of the nanowire is smooth.
According to the present invention, it is preferable that the gap width of the GaSb nanowire is reduced to 0.69eV due to the light doping of the tin catalyst.
According to the invention, preferably, the source electrode and the drain electrode are nickel electrodes, so that good ohmic contact with the GaSb nanowire is ensured; a further preferred nickel electrode thickness is 50 nm; preferably, the electrode spacing of the source and drain electrodes is 2-5 microns.
A high-performance infrared detector comprising the semiconductor device based on the GaSb nanowire with high hole mobility is disclosed.
The invention also provides a synthesis method of the GaSb nanowire with high hole mobility, which comprises the following steps:
growing by adopting a dual-temperature-zone vapor phase method, selecting metallic tin as a catalyst and a light doping source, wherein the dual-temperature zone comprises a source zone and a growth zone, and GaSb semiconductor powder is placed in the source zone and used for providing a source material; and the substrate covered with the tin metal catalyst is placed in the growth area and used for growing the nanowire.
According to the present invention, preferably, a surfactant is disposed between the source region and the growth region for modifying the nanowire.
According to the invention, preferably, the temperature interval of the source region is 730-780 ℃ and the temperature interval of the growth region is 530-570 ℃ during the growth of the nanowire, so that the decomposition and supply of the source material and the high-quality growth of the nanowire are ensured; the heat preservation growth time is 20-30 minutes, and after the growth is finished, the source region and the growth region are simultaneously stopped from heating and gradually cooled to the room temperature.
According to the invention, the preferred source material of the GaSb nanowire with high hole mobility is GaSb, the purity of the GaSb nanowire is 99.999 percent, the GaSb nanowire is in a powder form, and the particle size of the GaSb nanowire is less than or equal to 100 meshes;
preferably, the surfactant is a chalcogen, more preferably elemental sulfur, in powder form.
According to the present invention, the tin metal catalyst preferably has a thickness of 120-500 nm.
According to the invention, the growth system is preferably evacuated to 10 degrees before the growth of the GaSb nanowires-3After supporting, introducing carrier gas H2The purity is 99.999%, and the time for introducing the carrier gas is 20-40 minutes.
According to the invention, it is preferred that the GaSb source material is located at a distance of 15 cm from the substrate covered with the tin metal catalyst; the distance between the surfactant and the substrate covered with the tin metal catalyst was 9 cm.
The invention also provides a preparation method of the semiconductor device based on the GaSb nanowire with high hole mobility, which comprises the following steps:
transferring the grown GaSb nanowire with high hole mobility to Si/SiO through a liquid drop coating method2A substrate forming dispersed single nanowires;
preparing metal electrodes as source and drain by electron beam evaporation or thermal evaporation deposition process, Si/SiO2P-type silicon in the substrate serves as a grid;
and stripping by using the degumming agent to finish the preparation of the device of the semiconductor device.
According to the invention, the preparation method of the semiconductor device based on the GaSb nanowire with high hole mobility comprises the following steps:
(1) growing GaSb nanowires with high hole mobility by adopting a double-temperature-zone horizontal tube furnace: placing a boron nitride crucible containing GaSb powder in an upstream source region 15 cm away from a substrate for growing the nanowires, placing a substrate covered with 120-500 nm tin metal catalyst in a downstream growth region for growing the nanowires, placing the crucible containing surfactant sulfur powder between the two temperature regions, and placing the crucible 9 cm away from the substrate for growing the nanowires;
(2) pumping the pressure of the dual-temperature zone tube furnace system to 10-3After that, introducing carrier gas hydrogen with the purity of 99.999 percent for 20-40 minutes;
(3) raising the temperature of the source region to 730-780 ℃ and simultaneously raising the temperature of the growth region to 530-570 ℃, and preserving the temperature for 20-40 minutes;
(4) after the growth is finished, stopping heating the source region and the growth region, and gradually cooling to room temperature to complete the synthesis step of the GaSb nanowire;
(5) dispersing the synthesized GaSb nanowires into absolute ethyl alcohol, and transferring the nanowires to Si/SiO by a liquid drop coating method2A substrate forming dispersed nanowires;
(6) defining the source and drain electrode patterns of the device by an ultraviolet lithography technology, and performing the processes of spin coating, drying, exposure and development;
(7) evaporating 50 nanometer metal nickel as a source electrode and a drain electrode by an electron beam evaporation or thermal evaporation method;
(8) and stripping by using the degumming agent to finish the preparation of the semiconductor device.
According to the invention, a device with a single GaSb nanowire between a source electrode and a drain electrode is positioned by using a microscope, and a silicon substrate is used as a bottom gate electrode. The device can be tested for electrical performance and photoelectric performance by using a direct current probe station and a 1550 nanometer infrared laser.
The invention has not been described in detail, but is in accordance with the state of the art.
The invention firstly uses the chemical vapor deposition method and selects the metallic tin as the catalyst and the light doping source for growing the GaSb nanowire, and the field effect hole mobility of the GaSb nanowire is firstly improved to 1000cm2V-1s-1The infrared detection device with high responsivity and high performance and quick response time is prepared.
The invention has the beneficial effects that:
the invention realizes that the metal catalyst tin is lightly doped into the GaSb nanowire, thereby realizing the hole mobility of the nanowire, wherein the hole mobility exceeds 1000cm2V-1s-1And the forbidden band width is reduced to 0.69eV by regulating and controlling the energy band structure. The GaSb nanowire infrared detection device prepared by the micro-nano processing technology has strong process controllability and simple operation, has excellent photoelectric characteristics, shows good responsivity to infrared light of 1550 nanometers, and can reach 104Ampere/watt, and extremely fast response times, which can be as fast as several hundred microseconds.
Drawings
Fig. 1 is a schematic diagram illustrating a growth mechanism of the high hole mobility GaSb nanowire of the present invention, wherein tin is used as a catalyst and a light doping source.
Fig. 2 is a scanning electron microscope photograph of high hole mobility GaSb nanowires in example 1 of the present invention.
Fig. 3 is an electrical performance diagram of a single GaSb nanowire field effect transistor in test example 1 of the present invention, where fig. 3a is a transfer characteristic curve of a single GaSb nanowire field effect transistor, and fig. 3b is a statistical diagram of peak mobility of a single GaSb nanowire field effect transistor catalyzed by metal tin with different thicknesses.
Fig. 4 is a performance diagram of a GaSb nanowire infrared detection device with high hole mobility in experimental example 2 of the present invention, where fig. 4a is a schematic structural diagram of a single GaSb nanowire infrared detection device, fig. 4b is a scanning electron microscope photograph of the device, fig. 4c is a diagram of a change of photo-generated current and responsivity of the GaSb nanowire infrared detector with illumination intensity, and fig. 4d is a response time diagram of the GaSb nanowire infrared detection device.
Detailed description of the preferred embodiments
In order to illustrate the invention more clearly, the invention is further illustrated below by means of a specific embodiment and the accompanying drawings.
Example 1
By usingA double-temperature-zone horizontal tube furnace is characterized in that a boron nitride crucible containing 0.4 g of GaSb powder is placed in an upstream source zone and is 15 cm away from a sample, a crucible containing 0.5 g of surfactant sulfur powder is placed between the GaSb powder and a growth zone and is 9 cm away from the sample, and a Si/SiO film of a 120-nanometer metallic tin film is covered on the crucible2The substrate is arranged in the middle of the downstream temperature zone and is used as a catalyst and a light doping source for nanowire growth. The pressure of the tube furnace system is pumped to 10-3Hydrogen was passed through the reactor for 30 minutes at a purity of 99.999% with a flow rate of 200 sccm. The source region temperature was raised to 750 deg.c while the growth region temperature was raised to 550 deg.c for 25 minutes. And after the growth is finished, simultaneously stopping heating the source region and the growth region, and gradually cooling to room temperature to finish the step of synthesizing the GaSb nanowire with high hole mobility.
Si/SiO for preparing field effect transistor and infrared detector2Pre-treating the substrate, respectively ultrasonically cleaning the substrate with deionized water, acetone and ethanol, and drying. Dispersing the grown GaSb nanowire with high hole mobility into absolute ethyl alcohol by low-power ultrasonic, and transferring the GaSb nanowire into Si/SiO by a liquid drop coating method2And a substrate forming dispersed single nanowires.
The electrode position of the device is defined by ultraviolet photoetching technology, and the source electrode pattern and the drain electrode pattern are formed through processes of spin coating, glue drying, exposure and development, wherein the electrode distance is 2-5 microns. 50 nm of metallic nickel is evaporated by an electron beam evaporation or thermal evaporation method to be used as a source electrode and a drain electrode, and the evaporation rate is 0.2 nm/s. And stripping by using the degumming agent to finish the preparation steps of the field effect transistor and the high-performance infrared detector semiconductor device.
A device with a single GaSb nanowire between a source electrode and a drain electrode is positioned by using a microscope, a silicon substrate is used as a bottom gate electrode, and the device is tested for electrical performance by using a direct current probe platform to obtain an output and transfer characteristic curve; and testing the photoelectric performance of the device by using a 1550 nanometer infrared laser to obtain a photocurrent variation curve and a time response curve along with the source-drain voltage when the grid voltage is zero.
Example 2
The 200 nm metallic tin film is selected as a catalyst and a light doping source for growing the GaSb nanowire with high hole mobility, and other steps are the same as those in the embodiment 1.
Example 3
The 300 nm metallic tin film is selected as the catalyst and the light doping source for growing the GaSb nanowire with high hole mobility, and other steps are the same as those in the embodiment 1.
Example 4
The 400 nm metallic tin film is selected as a catalyst and a light doping source for growing the GaSb nanowire with high hole mobility, and other steps are the same as those in the embodiment 1.
Example 5
The 500 nm metallic tin film is selected as the catalyst and the light doping source for growing the GaSb nano-wire with high hole mobility, and other steps are the same as those in the embodiment 1.
Comparative example 1
As described in example 1, except that:
gold 0.1 nm thick was used as the catalyst. The grown gold-catalyzed GaSb nanowire is applied to a single nanowire field effect transistor, and the maximum peak value hole mobility is counted to be 400cm2V-1s-1。
Test example 1
The electrical properties of the single GaSb nanowire field effect transistors of examples 1-5 were tested as shown in fig. 3. Fig. 3a is a transfer characteristic curve of a single GaSb nanowire field effect transistor, and fig. 3b is a statistical graph of peak mobility of the single GaSb nanowire field effect transistor catalyzed by metallic tin with different thicknesses.
As can be seen from fig. 3, the single GaSb nanowire field effect transistor has excellent electrical properties. As can be seen from the transfer characteristic curve in fig. 3a, when the source-drain voltage is 0.1 v and the gate voltage is 2 v, the device has a higher source leakage current of 0.4 microampere; the threshold voltage is about 6.9-7.7 volts. From the data obtained from the statistics of peak mobility for a total of 150 devices in fig. 3b, it can be seen that the tin-catalyzed GaSb nanowires have ultra-high field effect mobility. The maximum peak mobility of the single GaSb nanowire field effect transistor catalyzed by metal tin with different thicknesses is 760cm respectively2V-1s-1,728cm2V-1s-1,780cm2V-1s-1,995cm2V-1s-1And 1028cm2V-1s-1. The reason for the significant increase in mobility is the light doping of the tin atoms, as well as the good crystallinity and effective surface passivation of the nanowires.
Test example 2
The schematic structural diagram and the scanning electron microscope photographs of the semiconductor device of the high hole mobility GaSb nanowire infrared detector in example 1 are shown in fig. 4a and b. Wherein, the source and drain electrodes are 50 nm metal nickel, the electrode spacing of the device in fig. 4b is 5 μm, and the diameter of the nanowire is 35 nm.
The performance of the high-performance GaSb single nanowire infrared detection device in example 1 is tested, as shown in fig. 4c and d. Fig. 4c is a graph of change of photo-generated current and responsivity of the GaSb nanowire infrared detection device with illumination intensity, and fig. 4d is a graph of response time of the GaSb nanowire infrared detection device. As can be seen from fig. 4, the GaSb nanowire infrared detection device based on high hole mobility has excellent photoelectric characteristics. For example: under the irradiation of 1550 nanometer infrared light, when the grid voltage is zero and the source-drain voltage is 1V, the photo-generated current of the GaSb single nanowire infrared detector exceeds 300 nanoamperes, and the responsivity exceeds 104Ampere/watt, response times of 143.4 microseconds and 237.0 microseconds, respectively.
The foregoing is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, it is possible to make several modifications and variations without departing from the technical principle of the present invention, so as to realize the controllable growth of nanowires and the preparation of infrared detection devices thereof in other research fields, and these modifications and variations should also be considered as the protection scope of the present invention.
Claims (7)
1. A semiconductor device based on GaSb nanowire with high hole mobility is characterized in that the semiconductor device comprises p-type silicon as a bottom gate electrode and Si/SiO2A channel composed of GaSb nanowire material between the source electrode and the drain electrode on the substrate, wherein the GaSb nanowire is doped with tin。
2. The semiconductor device based on the GaSb nanowire with high hole mobility as claimed in claim 1, wherein the diameter of the GaSb nanowire is 30-50 nanometers, and the length of the GaSb nanowire is more than or equal to 10 micrometers.
3. The GaSb nanowire-based semiconductor device with high hole mobility as claimed in claim 1, wherein the hole mobility of the GaSb nanowire may exceed 1000cm2V-1s-1The forbidden band width of the GaSb nanowire is reduced to 0.69 eV.
4. The high hole mobility GaSb nanowire-based semiconductor device according to claim 1, wherein the source and drain are nickel electrodes.
5. The high-hole-mobility GaSb nanowire-based semiconductor device according to claim 4, wherein the thickness of the nickel electrode is 50 nm, and the electrode distance between the source electrode and the drain electrode is 2-5 microns.
6. A high performance infrared detector comprising the high hole mobility GaSb nanowire-based semiconductor device according to any one of claims 1 to 5.
7. The method for manufacturing a semiconductor device based on high hole mobility GaSb nanowires of claim 1, comprising:
transferring the grown GaSb nanowire with high hole mobility to Si/SiO through a liquid drop coating method2A substrate forming dispersed single nanowires;
preparing metal electrodes as source and drain by electron beam evaporation or thermal evaporation deposition process, Si/SiO2P-type silicon in the substrate is used as a bottom gate electrode;
and stripping by using the degumming agent to finish the preparation of the semiconductor device.
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