CN117558833A - Preparation method of self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor - Google Patents
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- 230000005684 electric field Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002110 nanocone Substances 0.000 claims abstract description 28
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 15
- 238000005468 ion implantation Methods 0.000 claims abstract description 9
- 238000002161 passivation Methods 0.000 claims abstract description 9
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 7
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- 238000009792 diffusion process Methods 0.000 claims abstract description 5
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- 239000010931 gold Substances 0.000 claims description 10
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
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- 230000006798 recombination Effects 0.000 abstract description 14
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- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000004044 response Effects 0.000 abstract description 6
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- 238000000825 ultraviolet detection Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
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- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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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
- H01L31/18—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 Table
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- 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
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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 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
- H01L31/105—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PIN type
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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Abstract
The invention relates to the field of silicon-based ultraviolet photoelectric sensors, in particular to a preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor, which utilizes Bosch etching and plasma immersion etching to obtain a silicon nano cone with a micro-nano layered structure, so that surface reflection is effectively eliminated; forming shallow junctions by low-energy ion implantation; the aluminum oxide film is deposited by adopting a conformal atomic layer deposition technology in a diffusion enhancement mode, the high-quality deposited aluminum oxide film not only ensures effective passivation of the surface and effectively inhibits the defect recombination of a photogenerated carrier surface, but also introduces a negative charge enrichment layer to form a self-built external electric field to inhibit the carrier recombination loss and actively modulate the carrier movement, the light harvesting capability of the silicon nano cone is synergistically enhanced with the self-built external electric field introduced by aluminum oxide, the photogenerated electron hole pairs are collected more efficiently, and the ideal quantum efficiency and response speed are obtained while the detection range is expanded to the ultraviolet range.
Description
Technical Field
The invention relates to the field of silicon-based ultraviolet photoelectric sensors, in particular to a preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor.
Background
The ultraviolet detection technology has very wide application prospect in the aspects of space-based missile early warning, non-line-of-sight secret communication, hyperspectral investigation, space astronomical telescope, offshore fog breaking navigation, field fire remote sensing and other military and civil aspects. In the military aspect, the ultraviolet detection technology is mostly based on a 'solar blind area' in the near-earth atmosphere and an 'ultraviolet window' in the atmosphere, wherein the medium ultraviolet band can be used for ultraviolet alarming, early warning, communication, imaging auxiliary navigation, investigation and the like. Detection or guidance can be performed in the near ultraviolet band. In civil aspect, ultraviolet detection technology is increasingly important for rocket lifting track monitoring, falling track tracking after classifying rocket body separation, target star landing track recording and the like. At present, missile warning and arrow track monitoring technology based on solar blind area ultraviolet spectrum is most rapidly developed in various military and civil ultraviolet detection applications. However, in practical applications, there are a large number of gas molecules or dust with strong absorption and scattering capabilities for ultraviolet light, resulting in a very weak ultraviolet light signal that eventually reaches the detector. Therefore, it is important to improve the detection capability of the photoelectric device for weak ultraviolet light.
Nowadays, ultraviolet photoelectric sensors/photodiodes are mainly used for detecting ultraviolet rays with the wave band below 400nm, but widely used semiconductor photoelectric sensor devices have generally poor response to ultraviolet rays with the wave length of 200-300 nm, and the optimal detection sensitivity is still far below 80%. First, even under high energy ultraviolet excitation, one photon generates at most one "electron-hole" pair, and the remaining energy is eventually dissipated as thermal energy. Even with the proposed new carrier multiplication techniques, the External Quantum Efficiency (EQE) that determines the actual performance of the device is still quite low. Second, in unbiased photovoltaic mode, electrons excited by each incident uv photon energy cannot be fully collected. Some of the incident light energy is lost at the device surface due to reflection and another part is lost in the form of thermal energy due to recombination. The dissipation losses of these "light energy- > heat energy" are mainly due to the "defect point recombination" of the device surface structure and the "auger recombination" in the doped region forming the diode junction. It can be seen that there are two basic technical barriers to be solved in the current ultraviolet light electrical devices: (1) High surface reflection loss is difficult to eliminate and (2) high recombination loss of photogenerated carriers is difficult to suppress.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor, which combines a silicon nano cone substrate with high absorptivity with an aluminum oxide film, thereby solving the technical problems of low external quantum efficiency and low weak ultraviolet detection sensitivity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor provides a multi-dimensional silicon nano cone structure and aluminum oxide heterojunction, and expands the detection range of the photoelectric sensor to the ultraviolet range through light harvesting and self-built external electric field regulation and control coordination enhancement, so that the photoelectric sensor has ideal quantum efficiency and response speed, and the preparation method comprises the following steps:
s1, preparing a multidimensional silicon nano cone structure;
s2, performing ion implantation to form shallow junctions;
s3, heavily doping to form ohmic contact;
s4, magnetically sputtering a gold electrode;
s5, depositing an aluminum oxide film, wherein the aluminum oxide film is used as a passivation layer, and simultaneously a self-built external electric field is introduced, and the aluminum oxide film is conformally deposited above the silicon nano cone structure.
Further, in the step S1, the multidimensional silicon nano cone structure is formed by combining a micro structure and a nano structure; the micro-structures are subjected to photoetching to form corresponding patterns by adopting an MEMS (micro electro mechanical systems) process in advance, and then the corresponding micro-structures are formed by Bosch etching; the nano structure is a multidimensional silicon nano cone structure which is formed by adopting a photoetching process to form a corresponding pattern on the basis of a micron structure and then forming micro-nano layering through plasma immersion etching. The reflectivity of the silicon substrate is lower than that of the silicon substrate with a single structure, and the energy band structure is changed due to doping, so that the electron transition energy is reduced, and the absorption capacity is improved.
Further, in the step S2, the shallow junction is formed by ion implantation, the intrinsic layer I is provided by a high resistivity N-type (100) 4-inch silicon substrate, the P-type doped region is doped with low concentration boron, and the P-type doped region is located on the front surface of the silicon wafer, i.e. the surface of the silicon nano cone structure; the N-type doped region is doped with low-concentration phosphorus and is positioned on the back surface of the silicon wafer, namely the unstructured surface. The three components together form a PIN type photoelectric detector structure, when being irradiated by ultraviolet light, incident light is absorbed by the multidimensional silicon nanometer cone structure to generate photocurrent, and the information of a detection signal is obtained by detecting the magnitude of the photocurrent.
Further, in the step S3, the gold electrode is divided into an upper electrode and a lower electrode, the upper electrode is around the silicon nano cone structure, and the lower electrode is on the back of the silicon wafer.
Further, in the step S4, the ohmic contact is formed by doping boron and phosphorus above the upper electrode and below the lower electrode, respectively, and then annealing.
Further, in the step S6, a diffusion enhancement mode atomic layer deposition technology is adopted to deposit conformal alumina, so as to form an alumina film, and a heterojunction formed by alumina not only reduces surface recombination and plays a passivation role, but also generates an external electric field to accelerate separation of photon-generated carriers and reduce auger recombination; such a carrier collection enhancement structure can improve the collection efficiency of photogenerated carriers, thereby having higher response and quantum efficiency to ultraviolet light.
The invention determines the broad spectrum high absorption characteristic due to the unique micro-nano layered structure on the surface of the multidimensional silicon nano cone and the doped energy band structure, wherein the micro-nano layered structure generates a light trapping effect, the size is matched with the ultraviolet wavelength, the initial light absorption efficiency is improved, the energy band structure reduces the electron transition energy, the absorption capacity of a wider wave band is expanded, the aluminum oxide film not only ensures the effective passivation of the surface, effectively inhibits the defect recombination of the surface of a photon-generated carrier, but also introduces a negative charge enrichment layer, forms a self-built external electric field to inhibit the carrier recombination loss, actively modulates the carrier movement, the light harvesting capacity of the silicon nano cone and the self-built external electric field introduced by aluminum oxide are synergistically enhanced, the photon-generated electron hole pair is collected more efficiently, and the ideal quantum efficiency and response speed are obtained when the detected range is expanded to the ultraviolet range.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram of a design method of a silicon multidimensional silicon nano-cone substrate according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a design method of a silicon nano-cone conformal heterojunction according to an embodiment of the present invention;
the names corresponding to the reference numerals are: 1-silicon substrate, 2-multidimensional silicon nanometer cone structure and 3-alumina film.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
As shown in fig. 1-2, the invention provides a preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor, which comprises the steps of firstly patterning on the front surface of a high-resistance N-type silicon wafer by using a photoetching technology, obtaining a micro-structure on the front surface of the silicon wafer by using a Bosch etching method, then patterning by using photoetching, and etching the nano-structure on the basis of the micro-structure to obtain a multidimensional silicon nano-cone structure; the ion implantation method is to dope boron ions and phosphorus ions at low concentration on the front and back surfaces of the silicon wafer respectively; respectively ion heavily doping boron ions and phosphorus ions below a pre-designed upper electrode frame and a pre-designed lower electrode, and then performing magnetron sputtering on Ti and Au to respectively obtain an upper electrode and a lower electrode, wherein photoetching patterning is performed on the front surface of a silicon wafer, and annealing is performed to form ohmic contact; and then, adopting a conformal Atomic Layer Deposition (ALD) technology of a diffusion enhancement mode to deposit an alumina film, adopting a high-quality deposited alumina film to ensure effective passivation of the surface, effectively inhibiting defect recombination on the surface of a photogenerated carrier, simultaneously introducing a negative charge enrichment layer to form a self-built external electric field to inhibit carrier recombination loss, actively modulating carrier movement, and finally, scribing to obtain the silicon-based enhanced ultraviolet photoelectric sensor structure.
The following describes in detail the preparation process of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor according to a specific embodiment:
a) Preparing: selecting an N type (100) crystal face high resistivity (> 10KΩ cm) double polished silicon wafer with the thickness of 500+/-25 μm as a substrate 1;
b) Etching the micron grooves: adopting an HMDS vacuum oven coating technology, photoetching a corresponding pattern on a substrate by utilizing AZ5214 positive photoresist, and etching by using a Bosch etching process to obtain a micron structure with the height of about 20 mu m;
c) And (3) nanostructure etching: adopting an HMDS vacuum oven coating technology, photoetching a pattern corresponding to a micrometer structure on a substrate by utilizing AZ4620 positive photoresist, and carrying out plasma immersion etching to obtain a multidimensional silicon nano cone structure 2 with the height of about 4 mu m on the micrometer structure; wherein the multidimensional silicon nano cone structure 2 is formed by combining a micro structure and a nano structure; the micro-structures are subjected to photoetching to form corresponding patterns by adopting an MEMS (micro electro mechanical systems) process in advance, and then the corresponding micro-structures are formed by Bosch etching; the nano structure is a multidimensional silicon nano cone structure which is formed by adopting a photoetching process to form a corresponding pattern on the basis of a micron structure and then forming micro-nano layering through plasma immersion etching;
d) Doped region: adopting an ion implantation mode, doping boron ions at low concentration on the front side of the silicon substrate, doping phosphorus ions at low concentration on the back side of the silicon substrate, and then annealing at 950 ℃ for 30s for activation to obtain a PIN type structure formed by the P type doped region, the N type doped region and the (high-resistance silicon) substrate 1 together;
e) Electrode and ohmic contact: adopting an ion implantation mode, photoetching gold electrode patterns on a substrate by utilizing AZ5214 positive photoresist, doping boron ions on the front side, doping phosphorus ions on the back side, photoetching gold electrode patterns on the substrate by utilizing AZ4620 positive photoresist, adopting a magnetron sputtering process to deposit 50nmTi and 100nmAu, stripping upper gold electrodes around a silicon nano cone structure, adopting the same process parameters to obtain lower gold electrodes on the whole back side of the substrate, adopting a vacuum tube annealing furnace, and keeping annealing for 10min under the protection of nitrogen atmosphere at 350 ℃ to form ohmic contact;
f) Passivation layer: and depositing an aluminum oxide film 3 with the thickness of 20nm on the multidimensional silicon nano cone structure by adopting an Atomic Layer Deposition (ALD) mode in a diffusion enhancement mode, and simultaneously introducing a self-built external electric field into the aluminum oxide film 3 as a passivation layer to cover the upper part of the silicon nano cone structure in a conformal manner.
The self-built external electric field modulated silicon-based photoelectric sensor prepared by five steps of multidimensional silicon nano cone structure preparation, ion implantation to form shallow junction, heavy doping to form ohmic contact, magnetron sputtering of gold electrode and alumina film deposition has lower reflectivity than that of a silicon substrate with a single structure, and meanwhile, the energy band structure change caused by doping is reduced, and the electronic transition energy is improved in absorption capacity; the heterojunction formed by the aluminum oxide not only reduces surface recombination and plays a role in passivation, but also generates an external electric field to accelerate the separation of photogenerated carriers and reduce auger recombination; such a carrier collection enhancement structure can improve the collection efficiency of photogenerated carriers, thereby having higher response and quantum efficiency to ultraviolet light. The MEMS manufacturing process can be adopted to realize batch manufacturing, so that not only the low absorptivity of a single-structure silicon substrate is overcome, but also the high quantum efficiency and the responsivity of ultraviolet band are realized; is particularly suitable for detecting weak ultraviolet light.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (6)
1. A preparation method of a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing a multidimensional silicon nano cone structure;
s2, performing ion implantation to form shallow junctions;
s3, heavily doping to form ohmic contact;
s4, magnetically sputtering a gold electrode;
s5, depositing an aluminum oxide film, wherein the aluminum oxide film is used as a passivation layer, and simultaneously a self-built external electric field is introduced, and the aluminum oxide film is conformally deposited above the silicon nano cone structure.
2. The method for manufacturing the self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor as set forth in claim 1, wherein: in the step S1, the multidimensional silicon nano cone structure is formed by combining a micro structure and a nano structure; the micro-structures are subjected to photoetching to form corresponding patterns by adopting an MEMS (micro electro mechanical systems) process in advance, and then the corresponding micro-structures are formed by Bosch etching; the nano structure is a multidimensional silicon nano cone structure which is formed by adopting a photoetching process to form a corresponding pattern on the basis of a micron structure and then forming micro-nano layering through plasma immersion etching.
3. The method for preparing a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor as claimed in claim 1, wherein in the step S2, the shallow junction formed by ion implantation is a PIN structure, the intrinsic layer I is provided by a high-resistivity N-type (100) 4-inch silicon substrate, the P-type doped region is doped with low concentration boron and is positioned on the front surface of a silicon wafer, namely the surface of a silicon nano cone structure; the N-type doped region is doped with low-concentration phosphorus and is positioned on the back surface of the silicon wafer, namely the unstructured surface; the three components together form a PIN type photoelectric detector structure, when being irradiated by ultraviolet light, incident light is absorbed by the multidimensional silicon nanometer cone structure to generate photocurrent, and the information of a detection signal is obtained by detecting the magnitude of the photocurrent.
4. The method for preparing a self-built external electric field modulated silicon-based enhanced ultraviolet photoelectric sensor as claimed in claim 1, wherein in the step S3, the gold electrode is divided into an upper electrode and a lower electrode, the upper electrode is around the silicon nano cone structure, and the lower electrode is on the back of the silicon wafer.
5. The method for manufacturing a self-built external electric field modulated silicon-based enhanced uv sensor as claimed in claim 1, wherein in the step S4, the ohmic contact is formed by doping boron and phosphorus above the upper electrode and below the lower electrode, respectively, and then annealing.
6. The method for manufacturing a self-built external electric field modulated silicon-based enhanced ultraviolet photosensor as claimed in claim 1, wherein in step S6, a diffusion enhanced mode atomic layer deposition technique is used to deposit conformal alumina, thereby forming an alumina film.
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