CN114171609B - Heterojunction enhanced ultraviolet-visible light detector and preparation method and equipment thereof - Google Patents
Heterojunction enhanced ultraviolet-visible light detector and preparation method and equipment thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000003466 welding Methods 0.000 claims abstract description 50
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
- 238000001514 detection method Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000005485 electric heating Methods 0.000 claims abstract description 16
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002073 nanorod Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005476 soldering Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000005538 encapsulation Methods 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 238000000825 ultraviolet detection Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01L31/02—Details
- H01L31/02002—Arrangements for conducting electric current to or from the device in operations
- H01L31/02005—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier
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- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035227—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
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Abstract
The invention discloses a heterojunction enhanced ultraviolet-visible light detector, a preparation method and equipment thereof. The heterojunction enhanced ultraviolet-visible light detector comprises a detection chip, wherein the detection chip comprises a grounding electrode layer, a substrate layer, a titanium dioxide layer and a bias electrode layer which are sequentially arranged, and the titanium dioxide layer is a local doping layer; the bias electrode layer is a comb electrode layer, and a plurality of strip-shaped gaps are arranged at intervals so that external light irradiates the titanium dioxide layer. The heterojunction enhanced ultraviolet visible light detector is different from most of existing detectors, and the reverse opening type photoelectric detector realizes the reverse rotation characteristic of current. By controlling the wavelength and voltage range of the light, it is possible to achieve a photocurrent near zero and to achieve the inversion characteristic of the photodetector. The packaging equipment adopts the electric heating needle bar to weld the grounding electrode conducting plate and the bias electrode conducting plate, so that the central part of the detection chip is not affected by welding high temperature. And the integrated structure is adopted to complete the encapsulation of the detection chip, and the device has the characteristics of high efficiency, low cost and strong reliability.
Description
Technical Field
The invention relates to a visible light detector, in particular to a heterojunction enhanced ultraviolet-visible light detector, a preparation method and equipment thereof.
Background
The photoelectric detector can convert optical signals into electric signals, and has considerable application range and application prospect, in particular to various aspects such as biology, imaging, optical communication, industrial safety, military and the like. Currently, the preparation of a photodetection device having high sensitivity and high response speed in a specific light response band is one of important research directions in this field. Among them, uv-vis photodetectors show special potential in photo imaging, spectral analysis, environmental monitoring, spectroscopy, and visible light communication.
In recent years, technologies of photodetectors have been mature, and the characteristics of ultra-low dark current have been developed to make the photodetectors more widely used. However, the research on the reflective current detection mode of the reflective photoelectric detection device with the ultra-low photocurrent is not complete. The patent designs a local N-doped TiO based on the preparation method 2 The p-Si heterojunction enhances the ultraviolet-visible light detector, realizes the inversion characteristic of light response current, and enables the photocurrent of the device to be nearly zero by adjusting the wavelength of ultraviolet light or visible light and the magnitude of externally applied reverse bias voltage.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a heterojunction enhanced ultraviolet-visible light detector, a preparation method and equipment thereof.
The aim of the invention is achieved by the following technical scheme:
the heterojunction enhanced ultraviolet-visible light detector comprises a detection chip, wherein the detection chip comprises a grounding electrode layer, a substrate layer, a titanium dioxide layer and a bias electrode layer which are sequentially arranged, and the titanium dioxide layer is a local doping layer; the bias electrode layer is a comb electrode layer, and a plurality of strip-shaped gaps are arranged at intervals so that external light irradiates the titanium dioxide layer.
Preferably, the local doping layer is a local N-doping layer; the substrate layer is a p-type silicon substrate layer.
Preferably, the chip holder further comprises a chip holder for accommodating the detection chip, wherein the chip holder is provided with an accommodating cavity, the outer side of the grounding electrode layer is arranged at the bottom of the accommodating cavity, and the outer side of the chip holder is provided with a grounding electrode piece electrically connected with the grounding electrode layer and a bias electrode piece electrically connected with the bias electrode layer; the chip is characterized by further comprising a transparent layer arranged on the outer surface of the bias electrode layer, and the transparent layer is fixedly connected with the chip seat in a sealing mode.
Preferably, the strip-shaped gaps contain oxygen, and the concentration of the oxygen is 25% -30%.
Preferably, the bottom of the accommodating cavity of the chip seat is provided with a grounding electrode conducting groove communicated to the side surface and a grounding electrode conducting sheet arranged in the grounding electrode conducting groove, and the outer end of the grounding electrode conducting sheet is a roundabout part close to the bottom surface so as to form a grounding electrode sheet; a grounding electrode welding through hole which is communicated with the bottom surface of the accommodating cavity is drilled, and the grounding electrode conducting plate and the grounding electrode layer form reliable electric connection; the other side surface of the chip seat is provided with a bias electrode conducting groove and a bias electrode conducting sheet arranged in the bias electrode conducting groove, the outer end of the bias electrode conducting sheet is a detour part close to the bottom surface so as to form a bias electrode sheet, and the inner end of the bias electrode conducting sheet is a bias electrode welding part electrically connected with the bias electrode layer; the bias electrode solder forms a reliable electrical connection with the bias electrode layer.
The preparation method of the heterojunction enhanced ultraviolet visible light detector comprises the processing steps of a detection chip, and specifically comprises the following steps:
step S100, preprocessing the substrate layer, removing organic matters, metal ions and washing residues on the surface of the substrate layer, cleaning and drying;
step 200, firstly depositing Ti as a transition layer in an argon atmosphere for 1-5 min, and then depositing titanium dioxide in a mixed atmosphere of argon and ammonia in a ratio of 5:1-2:1 for 5-10 min, wherein the sputtering power is 20-50W;
step S300, calcining the substrate with the titanium dioxide obtained in the step S200 in an oxygen-containing atmosphere, and alloying and oxidizing; the calcination temperature is 400-600 ℃, namely, the crystallized titanium dioxide film is prepared on the substrate;
step S400, immersing the sample with the titanium dioxide seed crystal prepared in the step S300 into a mixed solution of deionized water, an HCl aqueous solution and tetra-n-butyl titanate; then carrying out hydrothermal reaction for 1-2 h at 100-200 ℃ to obtain an undoped titanium dioxide nanorod array grown on the surfaces of the silicon wafer and the glass;
step S500, nitriding the titanium dioxide nanorod array, which comprises the following substeps:
step S510, removing residual oxygen in the alumina tube, wherein the specific operation is as follows: ar and NH with the proportion of 95 percent to 5 percent are introduced into an alumina tube 3 Then keeping the temperature and the normal pressure for 30 to 50 minutes;
and step S520, placing the titanium dioxide nanorod array prepared in the step S400 into an alumina tube, then raising the temperature to 600-800 ℃, and performing heat treatment for 4-6 hours to prepare the local N-doped titanium dioxide/p-Si heterojunction.
Preferably, the method further comprises a chip seat packaging step S600, which comprises the following specific substeps:
step S610, a grounding electrode conducting groove communicated to the side surface and a grounding electrode conducting sheet arranged in the grounding electrode conducting groove are arranged at the bottom of the accommodating cavity of the chip seat, and the outer end of the grounding electrode conducting sheet is a roundabout part close to the bottom surface so as to form a grounding electrode sheet; the electric heating needle rod passes through the grounding electrode welding through hole to the grounding electrode conducting sheet and transfers heat to the grounding electrode conducting sheet so that soldering paste on the surface of the electric heating needle rod is melted and reliably electrically connected with the grounding electrode layer; the other side surface of the chip seat is provided with a bias electrode conducting groove and a bias electrode conducting sheet arranged in the bias electrode conducting groove, the outer end of the bias electrode conducting sheet is a detour part close to the bottom surface so as to form a bias electrode sheet, and the inner end of the bias electrode conducting sheet is a bias electrode welding part electrically connected with the bias electrode layer; the electrothermal needle bar is pressed and contacted with the welding part of the bias electrode, so that the soldering paste on the surface of the electrothermal needle bar is melted and reliably and electrically connected with the bias electrode layer;
step S620, placing the detection chip into the accommodating cavity of the chip seat, and welding between the bias electrode conductive hole and the bias electrode layer to form conductive connection of the bias electrode conductive hole and the bias electrode layer;
and step S630, after oxygen is filled into the accommodating cavity, the accommodating cavity is sealed by the transparent layer and is fixedly connected with the chip seat in a sealing manner.
The invention relates to a packaging device of a heterojunction enhanced ultraviolet visible light detector, which comprises a base, a chip seat moving guide rail, a detection chip feeding guide rail and a transparent layer feeding guide rail, wherein the chip seat moving guide rail, the detection chip feeding guide rail and the transparent layer feeding guide rail are arranged on the base; the chip seat moving guide rail is a longitudinal guide rail; the detection chip feeding guide rail and the transparent layer feeding guide rail are both transverse guide rails and are respectively positioned at the left side and the right side or the same side of the chip seat moving guide rail; a welding station is arranged between the feeding guide rail of the detection chip and the feeding guide rail of the transparent layer, and is used for welding the bias electrode conducting plate and the grounding electrode conducting plate; and a transparent layer bonding station is arranged on the discharging side of the transparent layer feeding guide rail so as to fix the transparent layer on the outer side of the accommodating cavity.
Preferably, the device further comprises a Gao Yangcang arranged on the base, the base is provided with an assembling sliding rail penetrating through the Gao Yang bin, the transparent layer bonding station is arranged in the Gao Yangcang, the Gao Yang bin is further provided with an oxygen input port, and the oxygen input quantity of the oxygen input port is larger than the outflow quantity of a gap around the Gao Yang bin so as to ensure the oxygen concentration in the high-oxygen bin.
Preferably, a jig table positioned on the assembling slide rail is further provided for fixing the chip holder; the jig table is driven by a conveyor belt arranged on the jig table and circularly moves; the jig table is provided with a mounting groove for mounting the chip seat, the bottom of the mounting groove is provided with a welding through hole, and when a welding station is used, an electric heating needle bar arranged at the bottom of the jig table penetrates through the welding through hole to finish welding between the grounding electrode layer and the grounding electrode conducting strip.
Compared with the prior art, the invention has the beneficial effects that: the heterojunction enhanced ultraviolet visible light detector is different from most of existing detectors, and the reverse opening type photoelectric detector realizes the reverse rotation characteristic of current. By controlling the wave of lightThe photoelectric detector has the advantages that the photoelectric detector has a long voltage range, the photocurrent is almost zero, the inversion characteristic of the photoelectric detector is realized, the application prospect in daily life is wide, the photoelectric detection performance is obviously improved, and the photoelectric detector is easier to use in applications involving portable and wearable equipment. Specifically 1. The material has higher quantum efficiency and response to ultraviolet detection, and also has larger rectification characteristic; 2. when proper reverse bias voltage and wavelength are controlled, the photocurrent of the device can be almost zero; 3. unlike most of the existing detectors, the reverse-opening photoelectric detector realizes the reverse characteristic of current. The preparation method of the heterojunction enhanced ultraviolet visible light detector utilizes a magnetron sputtering technology and a hydrothermal method to synthesize an almost vertical doped titanium dioxide nanorod array on the surface of P-type silicon, and prepares a local N-doped TiO 2 The p-Si heterojunction enhanced ultraviolet-visible light detector enables the photoelectric device to have higher quantum efficiency and response to ultraviolet detection, and also has larger rectification characteristic and lower photocurrent. The packaging equipment adopts the electric heating needle bar to weld the grounding electrode conducting plate and the bias electrode conducting plate, so that the central part of the detection chip is not affected by welding high temperature. And the integrated structure is adopted to complete the encapsulation of the detection chip, and the device has the characteristics of high efficiency, low cost and strong reliability.
Drawings
FIG. 1 is a schematic perspective view of a heterojunction-enhanced UV-visible light detector according to a first embodiment of the present invention (only a portion of the detection chip is shown);
FIG. 2 is a graph showing current characteristics when irradiated with ultraviolet light having a reverse bias of-0.03V and a wavelength of 340 nm;
FIG. 3 is a graph showing current characteristics when irradiated with ultraviolet light having a reverse bias voltage of-0.044V and a wavelength of 340 nm;
FIG. 4 is a graph showing different photocurrent response characteristics of the device under different reverse bias voltages when irradiated by ultraviolet light with a wavelength of 340 nm;
FIG. 5 is a graph showing different photocurrent response characteristics of the device under different wavelength ranges of illumination when reverse bias voltage is-0.02V;
FIG. 6 is a schematic cross-sectional view of a second embodiment of a heterojunction-enhanced UV-visible light detector of the present invention (with a positioning slot, only a detection chip portion is shown);
FIG. 7 is a schematic cross-sectional view of a second embodiment of a heterojunction-enhanced UV-visible light detector of the present invention;
FIG. 8 is a schematic cross-sectional view of the chip carrier in the embodiment of FIG. 7;
FIG. 9 is a schematic plan view of a heterojunction enhanced UV-visible light detector package apparatus of the present invention;
fig. 10 is a schematic cross-sectional view of the jig table in the embodiment of fig. 9.
Reference numerals
10. Positioning groove of detection chip 100
11. Bias electrode layer 12 titanium dioxide layer
13. Ground electrode layer of substrate layer 14
20. Chip holder 200 accommodating cavity
201. Bias electrode conductive slot 204 ground electrode conductive slot
209. Grounding electrode welding through hole 21 bias electrode conducting plate
210. Bias electrode plate 211 bias electrode welding part
24. Grounding electrode conductive sheet 240 grounding electrode sheet
241. Transparent layer at inner end 29 of grounding electrode
31. Chip seat moving guide rail 32 detects chip feeding guide rail
33. Slide rail for assembling transparent layer feeding guide rail 34
41. Bonding station 42
51. Gao Yangcang 60 jig table
61. Conveyor belt 600 mounting groove
601. Electric heating needle bar with welding through hole 62A
62B electric heating needle bar S detector
Detailed Description
The technical solutions of the present invention will be clearly and completely described below by the following examples, which are only some of the embodiments of the present invention, but not all of them. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention. As used in the specification of the embodiments of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As shown in FIG. 1, the heterojunction-enhanced UV-visible detector of the present invention (also referred to as a reverse-open type local N-doped TiO 2 The p-Si heterojunction enhanced ultraviolet visible light detector comprises a detection chip 10, wherein the detection chip comprises a grounding electrode layer 14, a substrate layer 13, a titanium dioxide layer 12 and a bias electrode layer 11 which are sequentially arranged, and the titanium dioxide layer 12 is a local doping layer; the bias electrode layer 11 is a comb electrode layer, and a plurality of strip-shaped gaps are formed at intervals to enable external light to irradiate the titanium dioxide layer 12.
The preparation method comprises the following steps:
first growing TiO on Si wafer surface 2 And the seed crystal, wherein the titanium source is tetra-n-butyl titanate. The substrate is pretreated, namely, organic matters on the surface of the substrate are removed,The metal ions and the washing residues are washed and dried,
in argon atmosphere, ti is used as a transition layer to deposit for 1-5 min, and then TiO is used as a transition layer 2 The ratio of argon to ammonia is 5: 1-2: 1 for 5-10 min, wherein the sputtering power is 20-50W; the obtained catalyst has TiO 2 Is calcined in an oxygen-containing atmosphere, and is alloyed and oxidized. The calcination temperature is 400-600 ℃, namely, the crystallized TiO is prepared on the substrate 2 A film. And then the prepared material with TiO 2 Immersing the sample of seed crystal in the mixed solution of deionized water, HCl aqueous solution and tetrabutyl titanate, and carrying out hydrothermal reaction at 100-200 ℃ for 1-2 h to obtain undoped TiO 2 An array of nanorods. The alumina tube is filled with the following components in percentage by weight: 5% Ar and NH 3 Then, the mixture is kept at room temperature and normal pressure for 30 to 50 minutes, and residual oxygen in the alumina tube is removed: the prepared TiO is treated by 2 The nano rod array is placed in an alumina tube, and then the temperature is raised to 600-800 ℃ for heat treatment for 4-6 hours, so as to prepare the local N-doped TiO 2 A p-Si heterojunction.
Then, the electrode layer is prepared by vacuum evaporation under a high vacuum environment.
FIG. 2 is a graph showing current characteristics when irradiated with ultraviolet light having a reverse bias of-0.03V and a wavelength of 340 nm. As can be seen from the figure, the current of the photodetector exhibits a negative value when no light is initially applied, i.e., in a dark environment, and a forward current is formed when light is increased, so that the photodetector exhibits a reverse characteristic of the light response current.
FIG. 3 is a graph showing current characteristics when irradiated with ultraviolet light having a reverse bias voltage of-0.044V and a wavelength of 340 nm. As can be seen from the figure, the photocurrent of the device is almost 0 at this time, and thus, zero photocurrent of the device can be achieved when appropriate reverse bias and wavelength are controlled.
Fig. 4 shows different photocurrent response characteristics exhibited by the device under different reverse bias voltages when irradiated with ultraviolet light having a wavelength of 340 nm. It can be seen that, within a certain range, the photocurrent gradually increases and the dark current gradually decreases with the decrease of the reverse bias voltage, and in addition, the reversal characteristic of the photocurrent response of the device can be seen in several curves. This phenomenon is also consistent with the description in principle.
Fig. 5 shows different photocurrent response characteristics exhibited by the device under different wavelength ranges of illumination conditions when reverse bias is-0.02V. It can be seen that, within a certain range, the wavelength of illumination is changed, the dark current is unchanged, but the photocurrent increases with the increase of the wavelength. In addition, the inversion characteristic of the photocurrent response of the device can be seen in several curves in the figure. This phenomenon is also consistent with the description in principle.
The structure of mutually restricting the double-junction photovoltaic effect is formed on the surface of the P-type silicon in an N local doping mode, and the reverse opening type photoelectric detection device with the photocurrent and dark current reversed (or the photocurrent returns to zero) is realized under the irradiation of light with specific wavelength.
As in the second embodiment of fig. 6, the detection chip of the heterojunction-enhanced uv-vis detector S of the present invention is further provided with a positioning groove 100. The detector S may be circular or square in shape. The positioning groove 100 may serve as a connection to the bias electrode conductive sheet or may serve as a positioning to prevent reverse installation, particularly when in a circular appearance. As shown in fig. 7-8, the chip holder 20 is further provided with a receiving cavity 200 for receiving the probe chip 10, the outside of the grounding electrode layer 14 is disposed at the bottom of the receiving cavity 200, and the outside of the chip holder 20 is provided with a grounding electrode plate 240 electrically connected with the grounding electrode layer 14 and a bias electrode plate 210 electrically connected with the bias electrode layer 11; the chip carrier further comprises a transparent layer 29 arranged on the outer surface of the bias electrode layer 11, and the transparent layer 29 is fixedly connected with the chip carrier 20 in a sealing mode. Wherein the strip-shaped gaps contain oxygen, and the concentration of the oxygen is 25% -30%.
More specifically, the bottom of the accommodating cavity 200 of the chip holder 20 is provided with a grounding electrode conductive groove 204 conducted to the side surface and a grounding electrode conductive sheet 24 arranged in the grounding electrode conductive groove 204, and the outer end of the grounding electrode conductive sheet 24 is a roundabout part close to the bottom surface so as to form a grounding electrode sheet 240; a ground electrode solder through hole 209 is drilled to allow the cavity to pass to the bottom surface, and the ground electrode inner end 241 of the ground electrode conductive tab 24 is in reliable electrical connection with the ground electrode layer 14. The other side surface of the chip seat 20 is provided with a bias electrode conducting groove 201 and a bias electrode conducting sheet 21 arranged in the bias electrode conducting groove 201, the outer end of the bias electrode conducting sheet 21 is a roundabout part close to the bottom surface to form a bias electrode sheet 210, and the inner end of the bias electrode conducting sheet 21 is a bias electrode welding part 211 electrically connected with the bias electrode layer 11; the bias electrode solder portion 211 forms a reliable electrical connection with the bias electrode layer 11.
In other embodiments, the depth of the positioning groove is gradually reduced from the ground electrode layer to the bias electrode layer so as not to interfere when the positioning groove is mounted on the chip carrier. The depth of the positioning groove at the position of the bias electrode layer is smaller than the length of the welding part 211 of the bias electrode protruding out of the accommodating cavity 200, so that the detection device 10 is placed in the accommodating cavity 200, and the welding part of the bias electrode is tightly matched with the bias electrode layer, so that the welding is firmer. More specifically, the positioning groove is provided with a plurality of convex teeth at the position of the bias electrode layer, so that when the detecting device 10 is placed in the accommodating cavity 200, the convex teeth are embedded into the tin-immersing layer of the welding part of the bias electrode to form an embedded connection relationship, and the bonding force is stronger during welding. The tooth shape is preferably triangular tooth shape.
In other embodiments, the ground inner end 241 is a sheet with at least one through hole having a diameter of 0.1-0.5 mm.
In the embodiment shown in fig. 9 to 10, the packaging device of the heterojunction-enhanced uv-vis photodetector of the present invention includes a base, a chip holder moving rail 31, a probing chip feeding rail 32, and a transparent layer feeding rail 33, which are disposed on the base; the chip holder moving guide rail 31 is a longitudinal guide rail; the detecting chip feeding guide rail 32 and the transparent layer feeding guide rail 33 are both transverse guide rails and are respectively positioned on the same side of the chip seat moving guide rail 31; a welding station 41 is arranged between the detecting chip feeding guide rail 32 and the transparent layer feeding guide rail 33, and is used for welding the bias electrode conducting plate and the grounding electrode conducting plate; a transparent layer bonding station 42 is also provided on the discharge side of the transparent layer feed rail 33 to secure the transparent layer to the outside of the receiving cavity.
The device also comprises a Gao Yangcang arranged on the base, the base is provided with a sliding rail 34 for assembly penetrating through the high-oxygen bin 51, the transparent layer bonding station 42 is arranged in the Gao Yangcang, the high-oxygen bin 51 is also provided with an oxygen input port, and the oxygen input quantity of the oxygen input port is larger than the outflow quantity of the peripheral gap of the Gao Yangcang so as to ensure the oxygen concentration in the high-oxygen bin.
A jig table 60 (fixed by a slider 69) located on the assembly slide rail 34 for fixing the chip carrier 20; the jig table 60 is driven by a conveyor belt 61 provided and moves in a cyclic manner; the jig table 60 is provided with a mounting groove 600 for mounting the chip holder 20, a welding through hole 601 is formed in the bottom of the mounting groove 600, and an electric heating needle bar 62A arranged at the bottom of the jig table 60 penetrates through the welding through hole 601 during a welding station so as to finish welding between the grounding electrode layer and the grounding electrode conductive sheet 24 (the grounding electrode sheet 240). An electrically heated pin 62B is also provided above the jig 60 at the welding station 41 for completing the welding of the bias electrode layer to the bias electrode conductive sheet 21 (bias electrode sheet 210). The electric heating needle bar 62A and the electric heating needle bar 62B are driven by the up-and-down movement mechanism, respectively.
Prior to assembly, the chip carrier 20 has completed the combination with the bias electrode conductive sheet 21, the ground electrode conductive sheet 24. The bias electrode conductive sheet 21 and the ground electrode conductive sheet 24 may be stamped from sheet metal. In order to avoid the need to apply solder to the bias electrode layer and the ground electrode layer, the bias electrode welding portion 211 and the ground electrode inner end 241 may be immersed in a layer of solder.
More specifically, to allow the jig table 60 to be recycled, the assembly rail 34 is extended back and forth and curved to the side, forming a closed rail structure. A receiving rail 35 is provided at the end of the assembly rail 34 remote from the chip carrier moving rail for receiving a packaged detector.
In order to increase the yield, in the embodiment of fig. 9, two packaged assembly rails 34 (and corresponding chip carrier moving rails, probing chip loading rails, transparent layer loading rails) are provided on a single frame, sharing the same high oxygen chamber 51. Because the length, width and height of the finished product of the heterojunction enhanced ultraviolet-visible light detector are about 10mm by 5mm. The occupied space is small, so that the output can be doubled by using the same machine seat.
In other embodiments, a feeding guide rail of the bias electrode conductive sheet and the ground electrode conductive sheet may be added in the feeding direction of the stand, and the bias electrode conductive sheet and the ground electrode conductive sheet may be mounted by a chip carrier without the bias electrode conductive sheet and the ground electrode conductive sheet. Such a packaging device can enable the chip carrier to be processed out of the die.
The invention also discloses a preparation method of the heterojunction enhanced ultraviolet visible light detector, which comprises the processing steps of a detection chip, and specifically comprises the following steps:
step S100, preprocessing the substrate layer, removing organic matters, metal ions and washing residues on the surface of the substrate layer, cleaning and drying;
step 200, firstly depositing Ti as a transition layer in an argon atmosphere for 1-5 min, and then depositing titanium dioxide in a mixed atmosphere of argon and ammonia in a ratio of 5:1-2:1 for 5-10 min, wherein the sputtering power is 20-50W;
step S300, calcining the substrate with the titanium dioxide obtained in the step S200 in an oxygen-containing atmosphere, and alloying and oxidizing; the calcination temperature is 400-600 ℃, namely, the crystallized titanium dioxide film is prepared on the substrate;
step S400, immersing the sample with the titanium dioxide seed crystal prepared in the step S300 into a mixed solution of deionized water, an HCl aqueous solution and tetra-n-butyl titanate; then carrying out hydrothermal reaction for 1-2 h at 100-200 ℃ to obtain an undoped titanium dioxide nanorod array grown on the surfaces of the silicon wafer and the glass;
step S500, nitriding the titanium dioxide nanorod array, which comprises the following substeps:
step S510, removing residual oxygen in the alumina tube, wherein the specific operation is as follows: ar and NH3 with the proportion of 95 percent to 5 percent are introduced into an alumina tube, and then the alumina tube is kept at room temperature and normal pressure for 30 to 50 minutes;
and step S520, placing the titanium dioxide nanorod array prepared in the step S400 into an alumina tube, then raising the temperature to 600-800 ℃, and performing heat treatment for 4-6 hours to prepare the local N-doped titanium dioxide/p-Si heterojunction.
More specifically, the method further includes a chip carrier packaging step S600, and the packaging apparatus in the embodiment of fig. 9-10 is adopted, including the following specific sub-steps:
step S610, a grounding electrode conducting groove communicated to the side surface and a grounding electrode conducting sheet arranged in the grounding electrode conducting groove are arranged at the bottom of the accommodating cavity of the chip seat, and the outer end of the grounding electrode conducting sheet is a roundabout part close to the bottom surface so as to form a grounding electrode sheet; the electric heating needle rod passes through the grounding electrode welding through hole to the grounding electrode conducting sheet and transfers heat to the grounding electrode conducting sheet so that soldering paste on the surface of the electric heating needle rod is melted and reliably electrically connected with the grounding electrode layer; the other side surface of the chip seat is provided with a bias electrode conducting groove and a bias electrode conducting sheet arranged in the bias electrode conducting groove, the outer end of the bias electrode conducting sheet is a detour part close to the bottom surface so as to form a bias electrode sheet, and the inner end of the bias electrode conducting sheet is a bias electrode welding part electrically connected with the bias electrode layer; the electrothermal needle bar is pressed and contacted with the welding part of the bias electrode, so that the soldering paste on the surface of the electrothermal needle bar is melted and reliably and electrically connected with the bias electrode layer;
step S620, placing the detection chip into the accommodating cavity of the chip seat, and welding between the bias electrode conductive hole and the bias electrode layer to form conductive connection of the bias electrode conductive hole and the bias electrode layer;
and step S630, after oxygen is filled into the accommodating cavity, the accommodating cavity is sealed by the transparent layer and is fixedly connected with the chip seat in a sealing manner.
In summary, the heterojunction enhanced ultraviolet-visible light detector is different from most of the existing detectors, and the reverse-opening photoelectric detector realizes the reverse characteristic of current. The photoelectric detector has the advantages that the photoelectric detector can realize the photoelectric current almost zero by controlling the wavelength and the voltage range of light, has wide application prospect in daily life, remarkably improves the photoelectric detection performance, and is easier to use in the application of portable and wearable equipment. Specifically 1. The material has higher quantum efficiency and response to ultraviolet detection, and also has larger rectification characteristic; 2. when proper reverse bias voltage and wavelength are controlled, the photocurrent of the device can be almost zero; 3. unlike most of the existing detectors, the reverse-opening photoelectric detector realizes the reverse characteristic of current. The preparation method of the heterojunction enhanced ultraviolet visible light detector utilizes a magnetron sputtering technology and a hydrothermal method to synthesize the almost vertical doped titanium dioxide nanorod array on the surface of the P-type silicon, so that the local N-doped TiO2/P-Si heterojunction enhanced ultraviolet visible light detector is prepared, so that the photoelectric device has higher quantum efficiency and response to ultraviolet detection, and simultaneously has larger rectification characteristic and lower photocurrent. The packaging equipment adopts the electric heating needle bar to weld the grounding electrode conducting plate and the bias electrode conducting plate, so that the central part of the detection chip is not affected by welding high temperature. And the integrated structure is adopted to complete the encapsulation of the detection chip, and the device has the characteristics of high efficiency, low cost and strong reliability.
The foregoing examples are provided to further illustrate the technical contents of the present invention for the convenience of the reader, but are not intended to limit the embodiments of the present invention thereto, and any technical extension or re-creation according to the present invention is protected by the present invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. The heterojunction enhanced ultraviolet-visible light detector is characterized by comprising a detection chip, wherein the detection chip comprises a grounding electrode layer, a substrate layer, a titanium dioxide layer and a bias electrode layer which are sequentially arranged, and the titanium dioxide layer is a local doping layer; the bias electrode layer is a comb-shaped electrode layer, and a plurality of strip-shaped gaps are formed at intervals so that external light irradiates the titanium dioxide layer;
the local doping layer is a local N-doped layer; the substrate layer is a p-type silicon substrate layer;
the chip holder is provided with a containing cavity, the outer side of the grounding electrode layer is arranged at the bottom of the containing cavity, and the outer side of the chip holder is provided with a grounding electrode piece electrically connected with the grounding electrode layer and a bias electrode piece electrically connected with the bias electrode layer;
the transparent layer is arranged on the outer surface of the bias electrode layer and is fixedly connected with the chip seat in a sealing mode;
the bottom of the accommodating cavity of the chip seat is provided with a grounding electrode conducting groove communicated to the side surface and a grounding electrode conducting sheet arranged in the grounding electrode conducting groove, and the outer end of the grounding electrode conducting sheet is a roundabout part close to the bottom surface so as to form a grounding electrode sheet; a grounding electrode welding through hole which is communicated with the bottom surface of the accommodating cavity is drilled, and the grounding electrode conducting plate and the grounding electrode layer form reliable electric connection; the other side surface of the chip seat is provided with a bias electrode conducting groove and a bias electrode conducting sheet arranged in the bias electrode conducting groove, the outer end of the bias electrode conducting sheet is a detour part close to the bottom surface so as to form a bias electrode sheet, and the inner end of the bias electrode conducting sheet is a bias electrode welding part electrically connected with the bias electrode layer; the bias electrode welding part and the bias electrode layer form reliable electric connection;
wherein, during processing, the proportion of the aluminum oxide tube is 95 percent: 5% Ar and NH3, then keeping the room temperature and the normal pressure for 30-50 min, placing the prepared TiO2 nanorod array in an alumina tube, and then raising the temperature to 600-800 ℃ for heat treatment for 4-6 hours to prepare the local N-doped TiO2/p-Si heterojunction.
2. The heterojunction-enhanced uv-vis photodetector of claim 1, wherein said strip-like voids contain oxygen in a concentration of 25% -30%.
3. The method for preparing the heterojunction enhanced ultraviolet visible light detector is characterized by comprising the processing steps of a detection chip, and specifically comprises the following steps:
step S100, preprocessing the substrate layer, removing organic matters, metal ions and washing residues on the surface of the substrate layer, cleaning and drying;
step 200, firstly depositing Ti as a transition layer in an argon atmosphere for 1-5 min, and then depositing titanium dioxide in a mixed atmosphere of argon and ammonia in a ratio of 5:1-2:1 for 5-10 min, wherein the sputtering power is 20-50W;
step S300, calcining the substrate with the titanium dioxide obtained in the step S200 in an oxygen-containing atmosphere, and alloying and oxidizing; the calcination temperature is 400-600 ℃, namely, the crystallized titanium dioxide film is prepared on the substrate;
step S400, immersing the sample with the titanium dioxide seed crystal prepared in the step S300 into a mixed solution of deionized water, an HCl aqueous solution and tetra-n-butyl titanate; then carrying out hydrothermal reaction for 1-2 h at 100-200 ℃ to obtain an undoped titanium dioxide nanorod array grown on the surfaces of the silicon wafer and the glass; step S500, nitriding the titanium dioxide nanorod array, which comprises the following substeps:
step S510, removing residual oxygen in the alumina tube, wherein the specific operation is as follows: ar and NH with the proportion of 95 percent to 5 percent are introduced into an alumina tube 3 Then keeping the temperature and the normal pressure for 30 to 50 minutes;
and step S520, placing the titanium dioxide nanorod array prepared in the step S400 into an alumina tube, then raising the temperature to 600-800 ℃, and performing heat treatment for 4-6 hours to prepare the local N-doped titanium dioxide/p-Si heterojunction.
4. A method of manufacturing as claimed in claim 3, further comprising a chip-carrier packaging step S600, comprising the specific sub-steps of:
step S610, a grounding electrode conducting groove communicated to the side surface and a grounding electrode conducting sheet arranged in the grounding electrode conducting groove are arranged at the bottom of the accommodating cavity of the chip seat, and the outer end of the grounding electrode conducting sheet is a roundabout part close to the bottom surface so as to form a grounding electrode sheet; the electric heating needle rod passes through the grounding electrode welding through hole to the grounding electrode conducting sheet and transfers heat to the grounding electrode conducting sheet so that soldering paste on the surface of the electric heating needle rod is melted and reliably electrically connected with the grounding electrode layer;
the other side surface of the chip seat is provided with a bias electrode conducting groove and a bias electrode conducting sheet arranged in the bias electrode conducting groove, the outer end of the bias electrode conducting sheet is a detour part close to the bottom surface so as to form a bias electrode sheet, and the inner end of the bias electrode conducting sheet is a bias electrode welding part electrically connected with the bias electrode layer; the electrothermal needle bar is pressed and contacted with the welding part of the bias electrode, so that the soldering paste on the surface of the electrothermal needle bar is melted and reliably and electrically connected with the bias electrode layer;
step S620, placing the detection chip into the accommodating cavity of the chip seat, and welding between the bias electrode conductive hole and the bias electrode layer to form conductive connection of the bias electrode conductive hole and the bias electrode layer;
and step S630, after oxygen is filled into the accommodating cavity, the accommodating cavity is sealed by the transparent layer and is fixedly connected with the chip seat in a sealing manner.
5. The packaging device of the heterojunction enhanced ultraviolet-visible light detector of claim 1, comprising a base, a chip seat moving guide rail, a detection chip feeding guide rail and a transparent layer feeding guide rail which are arranged on the base; the chip seat moving guide rail is a longitudinal guide rail; the detection chip feeding guide rail and the transparent layer feeding guide rail are both transverse guide rails and are respectively positioned at the left side and the right side or the same side of the chip seat moving guide rail; a welding station is arranged between the feeding guide rail of the detection chip and the feeding guide rail of the transparent layer, and is used for welding the bias electrode conducting plate and the grounding electrode conducting plate; and a transparent layer bonding station is arranged on the discharging side of the transparent layer feeding guide rail so as to fix the transparent layer on the outer side of the accommodating cavity.
6. The packaging device of claim 5, further comprising a housing Gao Yangcang provided with an assembly rail extending through the Gao Yang cartridge, wherein the transparent layer bonding station is provided in the housing Gao Yangcang, and wherein the housing Gao Yang is further provided with an oxygen inlet having an oxygen input greater than an outflow from a gap around the housing Gao Yang to ensure oxygen concentration in the high oxygen chamber.
7. The packaging apparatus of claim 6, further comprising a jig table located on the assembly slide for securing the chip carrier; the jig table is driven by a conveyor belt arranged on the jig table and circularly moves; the jig table is provided with a mounting groove for mounting the chip seat, the bottom of the mounting groove is provided with a welding through hole, and when a welding station is used, an electric heating needle bar arranged at the bottom of the jig table penetrates through the welding through hole to finish welding between the grounding electrode layer and the grounding electrode conducting strip.
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