CN111439722A - Micro-bolometer and preparation method thereof - Google Patents
Micro-bolometer and preparation method thereof Download PDFInfo
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- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
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- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
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- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
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- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
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Abstract
The invention discloses a microbolometer, which comprises a plane semiconductor crystalline nanowire array which is horizontally distributed, and an amorphous silicon layer and a silicon nitride layer which are sequentially laminated above the plane semiconductor crystalline nanowire array from bottom to top, wherein metal electrodes are arranged at two ends of the plane semiconductor crystalline nanowire. The invention changes the structure of the common microbolometer device at present, adopts the suspended crystalline state nano-wire as a support, and the suspended amorphous silicon (sensitive layer) silicon nitride (photosensitive layer), so that the detection island region can obtain thermal insulation well due to the limitation of the surface of the suspended crystalline state nano-wire on heat conduction, and meanwhile, the nano-wire has lower resistivity and can also be used as a conductive channel, thereby greatly improving the conversion from the thermal property to the electrical property of the device.
Description
Technical Field
The invention relates to a microbolometer and a preparation method thereof, in particular to a method for connecting and suspending an amorphous silicon nitride laminated film by utilizing a programmable crystalline state nanowire array, and particularly relates to a method for preparing a novel microbolometer device by utilizing the limitation of the surface of the suspended nanowire on heat conduction and the high thermal resistance coefficient of amorphous silicon.
Background
The infrared spectrum is classified into near infrared (wavelength range of 0.75 μm to 2.5 μm), mid infrared (wavelength range of 2.5 μm to 25 μm) and far infrared (wavelength range of 25 μm to 300 μm) according to the relationship between the infrared spectrum and visible light. The infrared spectrum has quite wide applicability to samples, can be applied to solid, liquid or gaseous samples, and can detect inorganic, organic and high molecular compounds; the infrared spectrum also has wide application in the research of the configuration, conformation and mechanical property of high polymers and the fields of physics, astronomy, meteorology, remote sensing, biology, medicine and the like. The traditional infrared spectrum detection system is a dispersion type infrared spectrum detection system, but the spectrum analysis system adopts single-channel measurement and has low scanning speed, thereby limiting the detection efficiency. The infrared detection means which is more commonly used in the market at present is a microbolometer. The specific principle is that the infrared light is converted into heat energy, and the resistance of the detector is further changed due to the change of the heat energy to perform characterization and detection. The thermosensitive microbolometer has the advantages of small volume, low cost, wide response wave band and mass production. Furthermore, the thermistor used in the patent is amorphous silicon, has a silicon process technology completely matched with the traditional industry, can greatly reduce the cost and can manufacture a large-scale array to improve the performance. Meanwhile, due to the limitation of the nanowire surface on heat conduction, the detection island region can obtain thermal insulation well, high-sensitivity infrared (> 2 mu m) micrometering radiation detection is facilitated, and efficient electric signal detection and reading are realized. The invention is beneficial to greatly reducing the preparation cost of the microbolometer device and improving the performance, and can be suitable for the application of flexible/stretchable electronic devices through the elastic appearance design.
According to the knowledge of the inventor, CN 102479879A discloses an amorphous silicon thermosensitive film, an uncooled amorphous silicon microbolometer and a preparation method thereof, and the patent adopts doped amorphous silicon as a thermistor, so that a wide process window can be provided and process fluctuation in the preparation process of the thermosensitive film can be overcome. CN101774530B discloses a microbolometer and a preparation method thereof, the thermosensitive material and the infrared absorption layer adopted by the patent are carbon nanotube-amorphous silicon composite film, which effectively improves the disadvantages of low conductivity and poor chemical stability of the traditional amorphous silicon thermistor thin film, and simultaneously avoids the negative effects of the traditional doping process on the amorphous silicon film. However, the structures adopted in the above two patents are still that the whole microbridge is directly laid on the cavity structure with the substrate of the readout circuit traditionally, so that the whole device still has great thermal conductance, and the minimum temperature that can be detected by the device is greatly reduced, and thus excellent detection performance cannot be obtained.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems and the defects in the prior art, the invention provides the microbolometer and the preparation method thereof, and provides a key technical basis for the application of the infrared detection field based on the planar semiconductor nanowire.
The technical scheme is as follows: a microbolometer, characterized by: the planar semiconductor crystalline nanowire array comprises a planar semiconductor crystalline nanowire array which is horizontally distributed, and an amorphous silicon layer and a silicon nitride layer which are sequentially laminated above the planar semiconductor crystalline nanowire array from bottom to top, wherein metal electrodes are arranged at two ends of the planar semiconductor crystalline nanowire array.
The technical scheme of the invention is that the metal electrode is PT-A L system, Ti-Au system or Ni metal material.
The invention also discloses a preparation method of the microbolometer, which is characterized by comprising the steps of growing a planar semiconductor crystalline nanowire array based on an IP-S L S growth method and combining with a step channel guide technology, regionally preparing an amorphous silicon and silicon nitride laminated connecting nanowire array above the crystalline nanowire array, defining and preparing metal electrodes at two ends of the nanowire array, and preparing the microbolometer.
The preparation method specifically comprises the following steps:
1) adopting a high-temperature-resistant support material as a substrate, and depositing an insulating medium layer on the substrate by using PECVD/PVD/CVD and other processes as a sacrificial layer;
2) defining a nanowire array guide pattern on a substrate, and preparing a guide channel by a dry etching technology or a wet etching technology;
3) taking the guide channel prepared in the step 2) as a substrate, and preparing a catalytic metal layer through photoetching, evaporation and sputtering processes;
4) putting a sample into PECVD (plasma enhanced chemical vapor deposition) to grow a planar crystalline nanowire array;
5) preparing an amorphous silicon and silicon nitride laminated layer in a regionalization mode above the planar nanowire array by utilizing photoetching and deposition or deposition and etching technologies, and connecting the nanowire array;
6) defining and preparing metal electrodes at two ends of the nanowire array by utilizing photoetching and evaporation technology;
7) spin-coating a layer of SU8 film on the surface of the substrate, defining a suspension area by using a photoetching method, and spin-coating a layer of photoresist film as a protective film of the nanowire array;
8) etching the sacrificial layer below the whole sample by using corrosive liquid to separate the SU8 film and all structures above the SU8 film from the substrate, wherein the SU8 film with patterned holes is used for supporting suspended nanowires, and the nanowires are used for supporting and suspending the amorphous silicon nitride lamination;
9) and removing the protective film by a solution method or dry etching to obtain the microbolometer device which is prepared by taking the crystalline nanowire as a support and suspending the amorphous silicon and the silicon nitride lamination.
The preparation method further defines the technical scheme as follows: the step 4) specifically comprises the following steps:
firstly, heating a reaction cavity to be higher than the melting point of catalytic metal, treating the catalytic metal by using plasma, removing an oxide layer on the surface of the catalytic metal and forming separated catalytic metal liquid drops;
secondly, reducing the temperature below the melting point of the catalytic metal, and covering an amorphous semiconductor film as a growth precursor;
and finally, in a non-oxygen environment, heating to a temperature higher than the melting point of the catalytic metal liquid drop, so that the front end of the catalytic metal liquid drop absorbs an amorphous layer, the rear end of the catalytic metal liquid drop deposits a crystalline nanowire, and the crystalline nanowire array grows along the step under the guidance of the step.
Preferably, the high-temperature-resistant supporting substrate is silicon wafer, glass, silicon nitride, silicon oxide, sapphire, ceramic wafer, quartz wafer, aluminum foil or plastic.
Preferably, in step 2), the guide channel is formed by making a guide pattern by photolithography, electron beam direct writing, and nanoimprint; the wet etching method is a wet etching technology of an alkaline corrosion system, an acidic corrosion system or an ethylenediamine pyrocatechol system; the dry etching adopts ICP-RIE technology.
Preferably, in step 3), the upper catalyst region is defined again using a photolithographic alignment technique, and a crystalline nanowire having a diameter of 130 ± 80nm is precisely grown along the guide channel by a planar nanowire guide growth method.
Preferably, in step 4), in a PECVD system, H is utilized2Plasma processing is carried out, an oxidation layer on the surface of the metal film is removed, the metal film is shrunk to form quasi-nano catalytic particles with the diameter of 100-2000nm, an amorphous layer with the thickness of 15-200nm is covered as a precursor layer, annealing is carried out in the environment with the temperature higher than the melting point of the metal in the non-oxygen atmosphere, the IPS L S growth mode is utilized, the nanowires are grown along the guide channel, and the crystalline nanowire array is obtained.
Preferably, in step 7), the protective film is PMMA, Az5214 or Az1500 photoresist.
Has the advantages that: compared with the prior art, the structure of the conventional microbolometer device is changed, the suspended crystalline-state nanowire is used as a support, the suspended amorphous silicon (sensitive layer) silicon nitride (photosensitive layer) is used as a light-sensitive layer, the surface of the suspended crystalline-state nanowire is limited in heat conduction, so that the detection island region can be well insulated thermally, and the nanowire has lower resistivity and can also be used as a conductive channel, so that the conversion from the thermal property to the electrical property of the device is greatly improved. This patent utilizes unsettled crystalline state nano wire as supporting amorphous silicon nitride film, and the microbolometer of preparation can effectively reduce the heat conduction, improves the detection and the reading of signal of telecommunication to unsettled nano wire accessible appearance design makes it can possess flexible tensile property, but wide application in infrared detection field.
Drawings
Fig. 1 is a flow chart of a process for manufacturing a microbolometer according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of an amorphous silicon microbolometer suspension in an embodiment of the present invention.
Fig. 3 is an optical microscope view of a suspended amorphous silicon microbolometer in an embodiment of the present invention.
Detailed Description
The invention is further elucidated with reference to the drawings and the embodiments.
As shown in fig. 2-3, the present embodiment discloses a microbolometer, which includes a planar semiconductor crystalline nanowire array 1 horizontally distributed, and an amorphous silicon layer 2 and a silicon nitride layer 3 sequentially stacked on the planar semiconductor crystalline nanowire array from bottom to top.
The metal electrodes can be PT (12 nm) -A L (80 nm) system, Ti-Au system, Ni and other metal materials, the metal contact can be improved by using a rapid thermal annealing process, and the evaporation method can use a thermal evaporation system, a magnetron sputtering system or an electron beam evaporation system.
The embodiment also discloses a preparation method of the microbolometer, which comprises the following specific steps as shown in figure 1:
1) the method comprises the following steps of (1) adopting a silicon wafer, glass, aluminum foil, silicon nitride, silicon oxide, silicon oxynitride, polymer or other metal materials as a substrate, and depositing an insulating medium layer on the substrate by utilizing a PECVD (plasma enhanced chemical vapor deposition) or PVD (physical vapor deposition) process;
2) defining a step guide pattern of the nanowire array by utilizing photoetching, electron beam direct writing or mask plate technology, and etching the dielectric layer by utilizing Inductively Coupled Plasma (ICP) etching or reactive plasma etching (RIE) process to form a vertical step side wall with the depth of about 150 +/-30 nm;
3) taking the grid step formed in the previous step as a substrate, and locally depositing a layer of banded catalytic metal layer by photoetching, evaporation or sputtering process;
4) raising the temperature in PECVD to be higher than the melting point of the catalytic metal, and introducing H2The reducing gas plasma is treated to convert the catalytic metal layer into separated metal nano-particles; reducing the temperature to below the melting point of the catalytic metal particles by using a PECVD system, and depositing and covering an amorphous semiconductor precursor film layer corresponding to the nanowire to be grown on the surface of the whole structure; then raising the temperature to be higher than the melting point of the metal, so that the nano metal particles are re-melted, an amorphous layer is absorbed at the front end of the nano metal particles, and a crystalline nano wire is deposited at the rear end of the nano metal particles; due to the guiding effect of the two-dimensional steps, the nanowires will grow along the steps;
5) the residual amorphous semiconductor precursor can be removed by etching processes such as hydrogen plasma, ICP or RIE;
6) depositing an amorphous silicon nitride laminated layer by using methods such as photoetching deposition and the like to connect the crystalline nanowire array;
7) defining an electrode area by using the steps of photoetching, evaporation, sputtering and the like, and evaporating a metal electrode;
8) spin-coating a layer of SU8 film on the surface of the substrate, defining a suspension area by photoetching and other methods, and spin-coating a layer of film again to prevent the crystalline nanowire from being broken by the surface tension of the liquid in the transfer process; etching the lower sacrificial layer of the whole sample by corrosive liquid to separate the SU8 film and all structural substrates on the SU8 film, wherein the SU8 film with patterned holes is used for suspending and supporting the crystalline nanowire which is used as a supporting suspended amorphous silicon nitride lamination;
9) and removing the protective film by using a solution method or a dry etching method, namely suspending the amorphous silicon nitride lamination by taking the crystalline nanowire as a support. The prepared microbolometer device can be widely applied to the field of infrared detection.
Preferably, in the step 2), the guide channel is used for manufacturing a guide pattern by methods such as photoetching, electron beam direct writing, nano-imprinting and the like; the etching method can be alkaline etching systems such as potassium hydroxide (KOH) and sodium hydroxide (NaOH), acidic etching systems such as hydrofluoric acid + nitric acid (HF + HNO3) and hydrofluoric acid + nitric acid + acetic acid (HF + HNO3+ CH3COOH), and wet etching technologies of systems such as ethylenediamine pyrocatechol (Ethylene diamine pyrocatechol); or dry etching techniques such as ICP-RIE.
Preferably, in step 3), the upper catalyst region is defined again by using the photolithography alignment technology, and the crystal nanowire with the diameter of 130 +/-80 nm is precisely grown along the guide channel by the planar nanowire guide growth method; the metal to be evaporated can be a low melting point metal of In, Sn, Bi, Ga and alloys thereof; the thickness is about 10-60 nm.
Preferably, in step 4), H is utilized in a PECVD system2The method comprises the steps of carrying out plasma treatment on reducing gas, removing an oxide layer on the surface of a metal film, enabling the metal film to be in a ball shape to form quasi-nanometer catalytic particles with the diameter of hundreds of nanometers to tens of micrometers, covering an amorphous layer with the thickness of 15-200nm as a precursor layer, annealing in an environment with the temperature of being higher than the melting point of metal in a non-oxygen atmosphere, and enabling nanowires to grow along a guide channel by utilizing an IPS L S growth mode to obtain a crystalline nanowire array.
Preferably, in step 8), the protective film may be a photoresist such as PMMA, Az5214, Az1500, or the like.
The invention adopts the IP-S L S method to grow the plane nano-wire, and combines the step channel guiding technology to grow the high-quality programmable plane semiconductor crystalline nano-wire, because the thermal conductivity of the suspended nano-wire is almost 0, and the amorphous silicon film has high temperature resistance coefficient, and is a good thermistor material, the thermal conductivity of the whole device is very small, and the invention has excellent infrared detection performance, and the method for preparing the micro-bolometer has wide prospect in the application aspects of infrared detection, sensors and the like.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (10)
1. A microbolometer, characterized by: the planar semiconductor crystalline nanowire array comprises a planar semiconductor crystalline nanowire array which is horizontally distributed, and an amorphous silicon layer and a silicon nitride layer which are sequentially laminated above the planar semiconductor crystalline nanowire array from bottom to top, wherein metal electrodes are arranged at two ends of the planar semiconductor crystalline nanowire array.
2. The microbolometer according to claim 1, wherein the metal electrode is a PT-A L system, a Ti-Au system or a Ni metal material.
3. A preparation method of a microbolometer is characterized by comprising the steps of growing a planar semiconductor crystalline nanowire array based on an IP-S L S growth method and combining a step channel guiding technology, preparing an amorphous silicon and silicon nitride laminated connection nanowire array in an area mode above the crystalline nanowire array, defining and preparing metal electrodes at two ends of the nanowire array, and preparing the microbolometer.
4. A method of making a microbolometer in accordance with claim 3, wherein: the method specifically comprises the following steps:
1) adopting a high-temperature-resistant support material as a substrate, and depositing an insulating medium layer on the substrate by using PECVD/PVD/CVD and other processes as a sacrificial layer;
2) defining a nanowire array guide pattern on a substrate, and preparing a guide channel by a dry etching technology or a wet etching technology;
3) taking the guide channel prepared in the step 2) as a substrate, and preparing a catalytic metal layer through photoetching, evaporation and sputtering processes;
4) putting a sample into PECVD (plasma enhanced chemical vapor deposition) to grow a planar crystalline nanowire array;
5) preparing an amorphous silicon and silicon nitride laminated layer in a regionalization mode above the planar nanowire array by utilizing photoetching and deposition or deposition and etching technologies, and connecting the nanowire array;
6) defining and preparing metal electrodes at two ends of the nanowire array by utilizing photoetching and evaporation technology;
7) spin-coating a layer of SU8 film on the surface of the substrate, defining a suspension area by using a photoetching method, and spin-coating a layer of photoresist film as a protective film of the nanowire array;
8) etching the sacrificial layer under the entire sample with a corrosive liquid such that the structure with the SU8 film and all structures above it are detached from the substrate;
9) and removing the protective film by a solution method or dry etching to obtain the microbolometer device which is prepared by taking the crystalline nanowire as a support and suspending the amorphous silicon and the silicon nitride lamination.
5. The method of manufacturing a microbolometer according to claim 4, characterized in that: the step 4) specifically comprises the following steps:
firstly, heating a reaction cavity to be higher than the melting point of catalytic metal, treating the catalytic metal by using plasma, removing an oxide layer on the surface of the catalytic metal and forming separated catalytic metal liquid drops;
secondly, reducing the temperature below the melting point of the catalytic metal, and covering an amorphous semiconductor film as a growth precursor;
and finally, in a non-oxygen environment, heating to a temperature higher than the melting point of the catalytic metal liquid drop, so that the front end of the catalytic metal liquid drop absorbs an amorphous layer, the rear end of the catalytic metal liquid drop deposits a crystalline nanowire, and the crystalline nanowire array grows along the step under the guidance of the step.
6. The method of manufacturing a microbolometer according to claim 4, characterized in that: the high-temperature-resistant supporting substrate is silicon chip, glass, silicon nitride, silicon oxide, sapphire, ceramic chip, quartz chip, aluminum foil or plastic.
7. The method of manufacturing a microbolometer according to claim 4, characterized in that: in the step 2), the guide channel is used for manufacturing a guide pattern by photoetching, electron beam direct writing and nano-imprinting methods; the wet etching method is a wet etching technology of an alkaline corrosion system, an acidic corrosion system or an ethylenediamine pyrocatechol system; the dry etching adopts ICP-RIE technology.
8. The method of manufacturing a microbolometer according to claim 4, characterized in that: in step 3), the upper catalyst region is defined again using the photolithographic alignment technique, and the crystalline nanowire with the diameter of 130 ± 80nm is precisely grown along the guide channel by the planar nanowire guide growth method.
9. The method of manufacturing a microbolometer according to claim 5, characterized in that: in step 4), in the PECVD system, H is utilized2Plasma processing is carried out, an oxidation layer on the surface of the metal film is removed, the metal film is shrunk to form quasi-nano catalytic particles, an amorphous layer with the thickness of 15-200nm is covered as a precursor layer, annealing is carried out in the environment with the temperature higher than the melting point of the metal in the non-oxygen atmosphere, the IPS L S growth mode is utilized, the nanowires are grown along the guide channel, and the crystalline nanowire array is obtained.
10. The method of making a microbolometer according to claim 1, characterized in that the steps comprise: in step 7), the protective film is PMMA, Az5214 or Az1500 photoresist.
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