CN111933749B - Preparation method of single crystal pyroelectric film multi-element infrared sensing device - Google Patents
Preparation method of single crystal pyroelectric film multi-element infrared sensing device Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 45
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 40
- 238000005530 etching Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 238000001259 photo etching Methods 0.000 claims abstract description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 15
- 238000001312 dry etching Methods 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 62
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 44
- 239000010409 thin film Substances 0.000 claims description 28
- 238000005468 ion implantation Methods 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 238000005459 micromachining Methods 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000009499 grossing Methods 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011282 treatment 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
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- G—PHYSICS
- 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
- G01J5/34—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using capacitors, e.g. pyroelectric capacitors
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—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
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Abstract
The invention belongs to the research field of infrared sensors, and relates to a preparation method of a single-crystal pyroelectric film multi-element infrared sensor. When the NiCr alloy is used as the upper electrode and the absorption layer, the invention realizes the preparation of the multi-element infrared sensing device by using the etching rate difference between the single crystal pyroelectric film and the NiCr alloy film as an etching mask. The method can finish the micro-processing of the multi-component device only by one-time photoetching, reduces the photoetching times of the single crystal film multi-component device, and avoids the difficulties of photoresist uniformity, alignment precision control and the like in multiple photoetching; the residual NiCr alloy film after the single crystal film is etched is used as an upper electrode and an absorption layer and does not need to be removed; and the NiCr alloy film generates a coarsening effect through dry etching, the reflection effect of the NiCr alloy film on infrared light is reduced, the absorption of the NiCr alloy film on infrared radiation is improved, and the performance of a device is further improved.
Description
Technical Field
The invention belongs to the research field of infrared sensors, and relates to a preparation method of a single-crystal pyroelectric film multi-element infrared sensor.
Background
With the continuous expansion of the application scenes of the pyroelectric infrared sensor, the demands of gesture recognition, position recognition, motion direction recognition, approximate imaging and the like on the multi-element infrared device are continuously increased, and higher requirements are provided for the performances of response time and the like of the multi-element infrared device. To meet the above application scenario and performance requirements, the use of pyroelectric film based multi-element infrared sensors is considered to be the best technical choice. Relevant researches show that the pyroelectric film single crystal prepared by the ion implantation stripping method breaks through the orientation and performance limitations of the film prepared by the traditional method, can obtain a high-performance pyroelectric single crystal film with the performance basically consistent with that of a single crystal bulk material, and provides a good material basis for the preparation of high-performance infrared devices.
As the sensitive material is developed from a block to a film and a device pixel from a unit to a plurality of elements, the device structure and the processing technology thereof also need to be correspondingly innovated to realize the preparation of the film multi-element device so as to fully exert the performance advantages of the film sensitive material.
Firstly, the traditional device structure is changed, and the block-based unit infrared sensor usually adopts thick film materials such as ink, activated carbon and the like deposited on an upper electrode structure as an absorption layer of the device. The thick film absorbing layer in the device structure has larger thickness, which obviously increases the heat capacity of the device and is not beneficial to exerting the characteristics of quick response and high-frequency detection rate of the thin film device. Meanwhile, the thick film absorption layer has larger photoetching line width, so that the area of the sensitive element is difficult to reduce, and the density of the sensitive element of the multi-element device is not easy to improve.
Secondly, the integrated multi-element infrared structure can be realized by the following two methods according to the sequence of patterning in the aspect of device technology: firstly, carrying out graphical dry etching on the pyroelectric film in a mask mode, and then graphically growing an upper electrode and an absorption layer to enable the upper electrode and the absorption layer to be just covered on the pyroelectric film which is not etched; secondly, the upper electrode and the absorption layer are firstly grown on the pyroelectric film layer in a graphical mode, and then the area where the upper electrode and the absorption layer are not grown is etched. Both methods require two masking steps, i.e., etching the mask and plating the electrode mask. However, in the two methods, before the mask is etched for the second time, a plurality of steps are formed on the surface of the device due to dry etching or growth of the upper electrode and the absorption layer, and the uneven surface of the device makes it difficult for the photoresist to be uniformly coated on the surface of the device; in addition, the masks of the photoresist for positive and negative twice need accurate photoetching alignment, the process is complex, and the operation difficulty is high.
Disclosure of Invention
Aiming at the problems or the defects, the method aims to solve the problem that the performance advantages of the thin film type multi-element infrared sensing device cannot be fully exerted based on the LTO single crystal block device structure and the micro-machining process; the invention provides a preparation method of a single crystal pyroelectric film multi-element infrared sensing device, which is characterized in that a NiCr alloy film is deposited on an LTO single crystal film stripped by ion implantation and is used as a structure of an upper electrode and an infrared absorption layer of the single crystal pyroelectric film multi-element infrared sensing device; in the aspect of device processing, by setting a proper thickness ratio of the NiCr film to the LTO single crystal film, the NiCr alloy film is etched as a dry etching mask to form a multi-element device sensitive element, and the absorption efficiency of the NiCr film layer on infrared radiation is improved by utilizing the coarsening effect of the etching process.
The technical scheme adopted by the invention for solving the technical problem is as follows:
step (1): and obtaining the LTO lithium tantalate single crystal thin film sheet by an ion implantation stripping method, wherein the LTO lithium tantalate single crystal thin film sheet comprises an LTO lithium tantalate pyroelectric layer, a bottom electrode, a bonding layer and a substrate from top to bottom.
Step (2): and (2) carrying out graphical photoetching mask on the upper surface of the pyroelectric layer of the LTO lithium tantalate single-crystal thin film sheet obtained in the step (1) through a micro-machining process.
And (3): and (3) growing a NiCr alloy film on one surface of the photoetching mask of the LTO lithium tantalate single crystal thin film sheet obtained in the step (2) by magnetron sputtering, and then removing the photoresist to obtain the patterned NiCr alloy film upper electrode.
And (4): and (4) carrying out dry etching on one surface of the upper electrode of the LTO lithium tantalate single-crystal thin film piece obtained in the step (3), and etching the LTO lithium tantalate pyroelectric layer uncovered by the upper electrode until the LTO lithium tantalate pyroelectric layer is etched to the bottom electrode.
Further, the specific preparation steps of the LTO lithium tantalate single crystal thin film sheet in the step (1) are as follows: taking an LTO lithium tantalate single crystal implanted wafer after ion implantation, and sequentially plating a bottom electrode and a bonding layer on the implanted surface of the implanted wafer; annealing the bonding layer of the injection sheet and the substrate to enable the injection sheet to be split along the highest damage layer strength position of ion injection to obtain an LTO lithium tantalate single crystal thin film sheet containing the LTO lithium tantalate pyroelectric layer, the bottom electrode, the bonding layer and the substrate, and then sequentially performing surface smoothing, cleaning and drying on the LTO lithium tantalate pyroelectric layer.
Further, the specific steps of patterning the lithography mask in the step (2) are as follows: and (2) realizing a photoresist mask on the LTO lithium tantalate single crystal thin film sheet obtained in the step (1) by adopting a reverse photoresist, wherein the pattern of the mask is the pattern of the upper electrode.
Further, the step (3) of determining the growth thickness of the NiCr alloy film comprises the following steps:
firstly, growing a NiCr alloy film with enough thickness by magnetron sputtering; etching the NiCr alloy film and the LTO lithium tantalate single chip simultaneously under the same etching condition; when the LTO lithium tantalate single chip is etched through, measuring the etching depth h1 of the NiCr alloy film; the thickness of the NiCr alloy film to be grown is h1+ h0, and h0 is the residual thickness of the NiCr after etching, namely the thickness of the NiCr alloy film when the NiCr alloy film is used as an upper electrode and an absorption layer of the integrated LTO multi-element infrared device.
When the NiCr alloy is used as the upper electrode and the absorption layer, the invention realizes the preparation of the multi-element infrared sensing device by using the etching rate difference of the single crystal pyroelectric film and the NiCr alloy film as an etching mask. The method can finish the micro-processing of the multi-component device only by one-time photoetching, reduces the photoetching times of the single crystal film multi-component device, and avoids the difficulties of photoresist uniformity, alignment precision control and the like in multiple photoetching; the residual NiCr alloy film after the etching of the single crystal film is used as an upper electrode and an absorption layer and does not need to be removed; and the NiCr alloy film generates a coarsening effect through dry etching, the reflection effect of the NiCr alloy film on infrared light is reduced, the absorption of the NiCr alloy film on infrared radiation is improved, and the performance of a device is further improved.
In conclusion, the integrated multi-element infrared structure preparation process for preparing the LTO single crystal film layer by the ion implantation stripping method is simple and easy to implement, the problems that photoresist related to secondary photoetching is difficult to uniformly coat and photoetching alignment requirements are high are solved, the cost is low, and the development of the ion implantation stripping method in the integrated direction in the pyroelectric infrared device is greatly promoted.
Drawings
FIG. 1 is a schematic structural diagram of a LTO lithium tantalate single-crystal thin film prepared by ion implantation delamination in step (1) of the example.
FIG. 2 is a schematic structural cross-sectional view of the LTO lithium tantalate single-crystal thin film after mask lithography in the step (2) of the embodiment.
FIG. 3 is a schematic structural cross-sectional view of the LTO lithium tantalate single-crystal thin-film sheet for forming a patterned upper electrode in step (3) of the example.
Reference numerals: 1-substrate, 2-bonding layer, 3-bottom electrode, 4-LTO lithium tantalate thermoelectric layer, 5-photoresist and 6-NiCr alloy film upper electrode.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and embodiments, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples of the present invention, those who do not specify specific conditions are performed according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The implementation of the technical scheme and the realization of the technical effect are not influenced by the raw materials of different manufacturers and models.
Example (b):
step (1) preparation of LTO lithium tantalate single crystal thin film: taking an LTO lithium tantalate single crystal implanted sheet after ion implantation, and sequentially plating a bottom electrode and a bonding layer on the implanted surface of the implanted sheet; annealing the bonding layer of the injection sheet and the substrate to enable the injection sheet to be split along the highest damage layer strength position of ion injection to obtain an LTO lithium tantalate single crystal thin film sheet containing the LTO lithium tantalate pyroelectric layer, the bottom electrode, the bonding layer and the substrate, and then sequentially performing surface smoothing treatment, cleaning and drying on the LTO thin film sheet. The structure is shown in fig. 1.
Step (2): and (2) carrying out patterned photoetching mask on the LTO lithium tantalate single crystal thin film sheet obtained in the step (1) through a micro-machining process, and realizing a photoresist mask by adopting a reverse photoresist, wherein the pattern of the mask is the pattern of an upper electrode, as shown in figure 2.
Step (3) firstly, determining the growth thickness of the NiCr alloy film: firstly, growing a NiCr alloy film with enough thickness by magnetron sputtering; etching the NiCr alloy film and the LTO lithium tantalate single chip simultaneously under the same etching condition; when the LTO lithium tantalate single chip is etched through, measuring the etching depth h1 of the NiCr alloy film; the thickness of the NiCr alloy film to be grown is h1+ h0, and h0 is the residual thickness of the NiCr after etching, namely the thickness of the NiCr alloy film when being used as an upper electrode and an absorption layer of the integrated LTO multi-element infrared device.
And (3) growing a NiCr alloy film with a determined thickness on the LTO film by using magnetron sputtering on the LTO lithium tantalate single crystal film sheet obtained in the step (2), and removing the photoresist to obtain a patterned NiCr alloy film, as shown in FIG. 3.
Claims (4)
1. A preparation method of a single crystal pyroelectric film multi-element infrared sensing device is characterized by comprising the following steps:
step (1): obtaining an LTO lithium tantalate single crystal thin film sheet by an ion implantation stripping method, wherein the LTO lithium tantalate single crystal thin film sheet comprises an LTO lithium tantalate pyroelectric layer, a bottom electrode, a bonding layer and a substrate from top to bottom;
step (2): carrying out graphical photoetching mask on the upper surface of the pyroelectric layer of the LTO lithium tantalate single-crystal thin film sheet obtained in the step (1) through a micro-machining process;
and (3): growing a NiCr alloy film on one surface of the photoetching mask of the LTO lithium tantalate single crystal thin film sheet obtained in the step (2) by magnetron sputtering, and then removing the photoresist to obtain a patterned NiCr alloy film upper electrode;
and (4): and (4) carrying out dry etching on one surface of the upper electrode of the LTO lithium tantalate single-crystal thin film sheet obtained in the step (3), and etching the LTO lithium tantalate pyroelectric layer uncovered by the upper electrode until the LTO lithium tantalate single-crystal thin film sheet is etched to the bottom electrode.
2. The method for preparing a single crystal pyroelectric thin film multielement infrared sensing device as claimed in claim 1, characterized in that:
the specific preparation steps of the LTO lithium tantalate single crystal thin film sheet in the step (1) are as follows: taking an LTO lithium tantalate single crystal implanted wafer after ion implantation, and sequentially plating a bottom electrode and a bonding layer on the implanted surface of the implanted wafer; annealing the bonding layer of the injection sheet and the substrate to enable the injection sheet to be split along the highest damage layer strength position of ion injection to obtain an LTO lithium tantalate single crystal thin film sheet containing the LTO lithium tantalate pyroelectric layer, the bottom electrode, the bonding layer and the substrate, and then sequentially performing surface smoothing, cleaning and drying on the LTO lithium tantalate pyroelectric layer.
3. The method for preparing a single crystal pyroelectric film multi-element infrared sensing device as claimed in claim 1, wherein:
the specific steps of patterning the photoetching mask in the step (2) are as follows: and (2) realizing a photoresist mask by using the LTO lithium tantalate single-crystal thin film obtained in the step (1) through a reverse photoresist, wherein the pattern of the mask is the pattern of the upper electrode.
4. The method for preparing a single crystal pyroelectric thin film multielement infrared sensing device as claimed in claim 1, characterized in that:
the step (3) further comprises a step of determining the growth thickness of the NiCr alloy film, and specifically comprises the following steps: firstly, growing a NiCr alloy film with enough thickness by magnetron sputtering; etching the NiCr alloy film and the LTO lithium tantalate single chip simultaneously under the same etching condition; when the LTO lithium tantalate single chip is etched through, measuring the etching depth h1 of the NiCr alloy film; the thickness of the NiCr alloy film to be grown is h1+ h0, and h0 is the residual thickness of the NiCr after etching, namely the thickness of the NiCr alloy film when being used as an upper electrode and an absorption layer of the integrated LTO multi-element infrared device.
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CN109216492A (en) * | 2018-08-16 | 2019-01-15 | 游代华 | A method of manufacture pyroelectric infrared detector sensing unit |
CN110952068A (en) * | 2019-11-20 | 2020-04-03 | 电子科技大学 | Preparation method of patterned single crystal thin film, patterned single crystal thin film and resonator |
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GB1545076A (en) * | 1976-01-16 | 1979-05-02 | Plessey Co Ltd | Pyro-electric detectors |
FR2649247B1 (en) * | 1989-06-30 | 1991-09-13 | Thomson Csf | INFRARED DETECTOR BASED ON PYROELECTRIC MATERIAL |
US20130320481A1 (en) * | 2012-06-01 | 2013-12-05 | Bridge Semiconductor Corporation | High Density Pyroelectric Thin Film Infrared Sensor Array and Method of Manufacture Thereof |
CN102903789B (en) * | 2012-07-09 | 2015-04-15 | 电子科技大学 | Preparation method of composite material infrared detector |
CN104409554A (en) * | 2014-11-28 | 2015-03-11 | 电子科技大学 | Carbon black absorbing layer-based pyroelectric infrared detector and manufacturing method thereof |
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