CN112379574A - Low-cost manufacturing method of terahertz photoconductive antenna with nano electrode - Google Patents
Low-cost manufacturing method of terahertz photoconductive antenna with nano electrode Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/427—Stripping or agents therefor using plasma means only
Abstract
The invention discloses a low-cost manufacturing method of a terahertz photoconductive antenna with a nano electrode, which combines nanoimprint with developing lateral etching to process double-layer glue in a reversed platform shape, and reduces the area of a metal film by using a metal baffle with a hole when a metal coating is prepared so as to solve the problem of difficult metal stripping when the nano electrode is processed by a lift-off process; meanwhile, a soft template which is copied from a hard template and can be used for multiple times is used, a nanometer electrode with submicron precision is processed through a nanometer imprinting technology, a main electrode with micron precision is processed through mask lithography, and therefore the processing speed of the terahertz photoconductive antenna is increased, the processing cost is reduced, and the terahertz photoconductive antenna is suitable for mass production.
Description
Technical Field
The invention relates to terahertz device processing, in particular to a method for manufacturing a terahertz photoconductive antenna with a nano electrode, which can reduce cost and realize mass production.
Background
Terahertz (THz) waves refer to electromagnetic radiation in the frequency range of 0.1-10THz, between infrared and microwave. Compared with other wave bands, the terahertz has low energy and coherence, carries abundant substance spectrum fingerprint characteristics, and has permeability on non-polar materials, so that THz radiation has great research value and application prospect in the fields of physics, chemistry, astronomy, safety inspection, wireless communication, medical science and the like. The generation of THz radiation is the key to the development and application of THz science and technology. Among a plurality of kinds of THz sources, the semiconductor-based terahertz photoconductive antenna has the advantages of low cost, compact structure, room-temperature operation and the like as a THz emission source. The terahertz photoconductive antenna is a device which is formed by plating gold on a semiconductor material such as gallium arsenide grown at low temperature to form an electrode and an antireflection film and can be used as a terahertz source or a terahertz detector. The nano electrode is manufactured in an electrode gap region (illumination region) of the photoconductive antenna, so that surface plasmon resonance can be generated on pump light, the concentration of photon-generated carriers can be regulated, and the transmitting power or the detection sensitivity of the terahertz antenna can be improved.
The existing terahertz photoconductive antenna with the nano-electrode needs two different processing accuracies, so that step-by-step processing needs to be carried out in two ways, namely, the nano-electrode with submicron accuracy is manufactured through electron beam exposure, and the main electrode part of the antenna with micron accuracy is processed through mask lithography. The defects that the electron beam exposure processing of a 2-inch wafer needs hundreds of thousands of units, takes hundreds of hours, has low electron beam exposure processing speed and high cost, are mainly used for scientific research and prototype manufacture, and are not beneficial to batch production. The nano-imprinting technology can process submicron-scale patterns, has the advantage of low average cost (although the first template for nano-imprinting needs to be exposed by an electron beam, the template can be used hundreds or even thousands of times, so that the cost is shared), and is suitable for large-scale production. However, in the nanoimprint process, the template is vertically pressed downwards and then vertically lifted during demolding, so that the side walls of the patterns left on the nanoimprint glue are vertical or trapezoidal, and the reverse-table-shaped nanoimprint glue cannot be formed. When the glue with the non-inverted platform shape is processed and prepared by using a lift-off process, the defects that the metal thickness cannot be too thick and the metal is difficult to strip exist. At present, no report of introducing a nano-imprinting technology into the processing of the terahertz photoconductive antenna is found.
Disclosure of Invention
In order to overcome the defects of high cost and low speed of electron beam exposure, the invention uses nano-imprinting to replace electron beam exposure, reduces the processing cost, improves the processing speed, and solves the problem that metal is difficult to strip when the lift-off process is applied to the conventional nano-imprinting by combining the nano-imprinting with developing side etching to process double-layer glue in the shape of an inverted platform.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-cost manufacturing method of a terahertz photoconductive antenna with a nano electrode comprises the following steps:
(1) spin-coating a layer of positive photoresist on a gallium arsenide wafer prepared by low-temperature growth, wherein the thickness of a glue film is 30-60nm, and then baking for 60-80s at 80-110 ℃;
(2) spin-coating a layer of nano-imprint glue on the baked wafer, wherein the thickness is 150-250 nm;
(3) carrying out heat-assisted ultraviolet imprinting by using a soft template with a submicron precision nano-electrode pattern structure, transferring the pattern of the nano-electrode to an adhesive film, and removing the soft template;
(4) removing the nano imprinting glue and the positive photoresist in the imprinting groove by using an oxygen plasma etching technology to expose the gallium arsenide wafer;
(5) rinsing with 1wt% KOH solution, laterally dissolving off part of the photoresist to obtain a double-layer adhesive film in a reversed stage shape in the nano electrode area, and then baking for 60s at 80-110 ℃ by using a hot plate; the difficulty of stripping and removing the photoresist of the metal in the lift-off process can be greatly reduced through the step;
(6) after covering the range outside the nano electrode area by using a metal baffle with an opening, sequentially plating a Ti plating layer with the thickness of 10-100nm and an Au plating layer with the thickness of 50-140nm (the total thickness of the Ti plating layer and the Au plating layer cannot exceed 150 nm) in the nano electrode area by magnetron sputtering or electron beam evaporation technology, then removing the metal baffle, carrying out lift-off process by using organic solution ultrasonic heating such as chlorobenzene, acetone and the like, and then carrying out rapid high-temperature annealing at 450 ℃ for 15s to form ohmic contact to obtain a wafer with a nano electrode structure;
(7) spin-coating a layer of negative photoresist on the wafer with the nano-electrode structure obtained in the step (6), wherein the thickness of the negative photoresist is 1.5-3 μm, and performing operations such as exposure, development, post-baking and the like by using a conventional photoetching plate with an antenna main electrode and a metal pad pattern with micron-scale precision according to a conventional process to transfer the antenna main electrode part and the metal pad pattern onto the negative photoresist;
(8) sequentially plating a Ti plating layer with the thickness of 10-100nm and an Au plating layer with the thickness of 200-900nm (the total thickness of the Ti plating layer and the Au plating layer is 300-1000 nm) on the whole wafer by magnetron sputtering or electron beam evaporation technology, then carrying out lift-off process by using organic solution ultrasonic heating such as chlorobenzene, acetone and the like, and then carrying out rapid high-temperature annealing at 450 ℃ for 15s to obtain the wafer simultaneously containing the nano-electrode, the antenna main electrode and the metal pad structure;
(9) plating a layer of silicon nitride or silicon oxide film on the wafer obtained in the step (8) by using chemical vapor deposition (PECVD), wherein the thickness of the silicon nitride or silicon oxide film is measured by the infrared ray capable of increasing the reflection of 880nm wave bands;
(10) spin-coating a layer of positive photoresist on the wafer obtained in the step (9) to form a positive photoresist layer with the thickness of 1-3 μm, then performing exposure, development, post-baking and other operations by using a photoetching plate with the same pattern as the metal pad structure on the wafer according to a conventional process, so that a metal pad area is presented on the positive photoresist layer, removing the photoresist on the metal pad area, etching the silicon nitride or silicon oxide film in the metal pad area by using a Reactive Ion Etching (RIE) technology, and finally cleaning the positive photoresist layer by using a photoresist solution to obtain a complete antenna structure;
(11) and (2) the antenna structure is cleaved and cut from the wafer, the silicon lens and the sleeve tube seat are adhered by epoxy resin, and then two different electrodes connected with the antenna are connected to the AlN substrate or the PCB substrate by gold wire drilling on the metal bonding pad, so that the terahertz photoconductive antenna with the nano electrode is prepared.
The soft template used in the step (3) is prepared by taking a conventionally used hard template as a master template and reprinting the master template by adopting polymer materials such as polydimethylsiloxane (DMS), polyvinyl alcohol (PVA), polyvinyl chloride (PVC) and the like, and a set of hard template can reprint hundreds or even thousands of sets of soft templates, so that the use times of the hard template is improved, and the processing cost is reduced.
The invention has the following remarkable effects:
according to the invention, nanoimprint lithography and developing side etching of the double-layer adhesive are combined to prepare the double-layer adhesive with the inverted structure, and after the metal is plated on the nano electrode region by utilizing the metal baffle with the opening, stripping liquid cannot be blocked due to a gap (as shown in a figure 1 d) between the metal and the photoresist, so that the method is very beneficial to later-stage metal stripping and residual adhesive removal. Meanwhile, the nanometer electrode part with submicron precision is manufactured by a nanometer stamping technology, and then the main electrode part, the metal pad part and the antireflection film part with micron precision are processed by an ultraviolet photoetching machine, so that the overall processing speed is improved.
Drawings
Fig. 1 is a schematic flow chart (side view) of the present invention for preparing a nano-electrode structure on a gaas wafer by nanoimprint, wherein (a) S1805 positive photoresist and nanoimprint resist are spin-coated in sequence; (b) imprinting by using a soft template; (c) the double-layer adhesive film is a double-layer adhesive film with a reversed structure formed by oxygen plasma etching and KOH solution rinsing; (d) plating Ti and Au on the nano electrode area; (e) the chip is provided with a nano electrode structure.
Fig. 2 is a schematic view (top view) of a complete antenna structure made in accordance with the present invention.
Fig. 3 is a schematic view (front view) of a completed antenna structure prepared by the present invention after being bonded to a silicon lens.
Fig. 4 is a diagram of a finished product of the terahertz photoconductive antenna prepared by the present invention.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
Cleaning a gallium arsenide wafer prepared by low-temperature growth, spin-coating a layer of S1805 positive photoresist glue solution with the concentration of 20wt% and the thickness of 60nm, baking the glue solution for 60 seconds by using a hot plate at the temperature of 95 ℃, and then spin-coating a layer of nano imprinting glue and the thickness of 200 nm. And (2) pre-copying by using a conventional hard template to prepare a DMS soft template with a submicron-precision nano electrode pattern structure, then carrying out heat-assisted ultraviolet imprinting by using the DMS soft template, transferring the submicron-precision nano electrode pattern to a glue film, and removing the soft template. And removing the nano imprinting glue and the S1805 positive photoresist in the imprinting groove by using an oxygen plasma etching technology to expose the gallium arsenide wafer. Rinsing with 1wt% KOH solution for 9 seconds to laterally dissolve part of the photoresist to obtain a double-layer adhesive film in a reverse mesa shape in the nano-electrode region, and then baking on a hot plate at 95 ℃ for 60 seconds. Covering the area outside the nano electrode area by using a metal baffle with an opening, sequentially plating a Ti plating layer with the thickness of 20nm and an Au plating layer with the thickness of 100nm in the nano electrode area of the wafer by using an electron beam evaporation technology, then removing the metal baffle, carrying out lift-off process by using organic solution such as chlorobenzene, acetone and the like through ultrasonic heating, and then carrying out rapid high-temperature annealing at the temperature of 420 ℃ for 15s to obtain the wafer with the nano electrode structure. Spin-coating a layer of AZ5214 negative photoresist on the obtained wafer, wherein the thickness is 2 microns, performing an inversion process by using a conventional photoetching plate with a micron-sized precision antenna main electrode and a metal pad pattern, transferring the patterns of the antenna main electrode and the metal pad pattern onto the photoresist, plating a layer of Ti with the thickness of 20nm and a layer of Au with the thickness of 600nm on the whole wafer by an electron beam evaporation technology, performing a lift-off process by using organic solutions such as chlorobenzene and acetone through ultrasonic heating, and performing rapid high-temperature annealing at the temperature of 420 ℃ for 15s to obtain the wafer simultaneously containing three metal structures of the nano electrode, the antenna main electrode and the metal pad. A silicon nitride film is plated on a wafer containing three metal structures by PECVD (plasma enhanced chemical vapor deposition) and used for increasing the transmission of pump light in a 880nm wave band, a layer of S1828 positive photoresist is spun, the thickness of the positive photoresist is 3 mu m, a photoetching plate with the same graph as that of the metal pad structure on the wafer is used for carrying out conventional operations such as exposure, development, post-baking and the like, so that a metal pad area is presented on the positive photoresist, then the photoresist of the metal pad area is removed, the silicon nitride film of the metal pad area is etched by RIE (reactive ion etching), and finally the photoresist is cleaned by the photoresist solution, so that the complete antenna structure is obtained. And (3) the antenna structure is cleaved and cut from the wafer, the silicon lens and the sleeve tube seat are adhered by epoxy resin, and then two different electrodes connected with the antenna are connected to the AlN substrate by gold wires on the metal bonding pad, so that the terahertz photoconductive antenna with the nano electrode is prepared.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A low-cost manufacturing method of a terahertz photoconductive antenna with a nano electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) spin-coating a layer of positive photoresist on a gallium arsenide wafer prepared by low-temperature growth, and then baking;
(2) spin-coating a layer of nano-imprint glue on the baked wafer;
(3) carrying out heat-assisted ultraviolet imprinting by using a soft template with a submicron precision nano-electrode pattern structure to transfer the pattern of the nano-electrode to an adhesive film, and then removing the soft template;
(4) removing the nano imprinting glue and the positive photoresist in the imprinting groove by using an oxygen plasma etching technology to expose the gallium arsenide wafer;
(5) rinsing with 1wt% KOH solution to obtain a double-layer adhesive film in a reversed stage shape in the area of the nano electrode, and then baking for 60s at a hot plate at 80-110 ℃;
(6) covering the range outside the nano electrode area by using a metal baffle with an opening, sequentially plating a layer of Ti and a layer of Au in the nano electrode area by using a magnetron sputtering or electron beam evaporation technology, then removing the metal baffle, carrying out lift-off process by using organic solution ultrasonic heating, and then carrying out rapid high-temperature annealing at 450 ℃ for 15s to obtain a wafer with a nano electrode structure;
(7) spin-coating a layer of negative photoresist on the wafer with the nano-electrode structure obtained in the step (6), and performing exposure, development and postbaking by using a photoetching plate with the patterns of the antenna main electrode and the metal pad with micron-scale precision according to a conventional process to transfer the patterns of the antenna main electrode and the metal pad onto the negative photoresist;
(8) plating a layer of Ti and a layer of Au on the whole wafer in sequence by magnetron sputtering or electron beam evaporation technology, then carrying out lift-off process by using organic solution ultrasonic heating, and then carrying out rapid high-temperature annealing at 450 ℃ for 15s to obtain a wafer simultaneously containing a nano electrode, an antenna main electrode and a metal pad structure;
(9) plating a silicon nitride or silicon oxide film capable of increasing the transmission of 880nm infrared rays on the wafer obtained in the step (8) by using a chemical vapor deposition method;
(10) spin-coating a layer of positive photoresist on the wafer obtained in the step (9), then using a photoetching plate with the same graph as the metal bonding pad structure on the wafer to perform exposure, development and post-baking according to a conventional process, so that a metal bonding pad area appears on the positive photoresist, removing the photoresist on the metal bonding pad area, etching the silicon nitride or silicon oxide film on the metal bonding pad area by using a reactive ion etching technology, and finally cleaning the positive photoresist by using a photoresist solution to obtain a complete antenna structure;
(11) and (2) the antenna structure is cleaved and cut from the wafer, the silicon lens and the sleeve tube seat are adhered by epoxy resin, and then two different electrodes connected with the antenna are connected to the AlN substrate or the PCB substrate by gold wire drilling on the metal bonding pad, so that the terahertz photoconductive antenna with the nano electrode is prepared.
2. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: in the step (1), the thickness of the adhesive film is 30-60 nm; the baking temperature is 80-110 ℃, and the baking time is 60-80 s.
3. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the thickness of the spin-coating nano-imprint glue in the step (2) is 150-250 nm.
4. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the soft template used in the step (3) is made by reprinting a polymer material from a hard template, wherein the polymer material comprises any one of polydimethylsiloxane, polyvinyl alcohol and polyvinyl chloride.
5. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: in the step (6), the thickness of the Ti plating layer is 10-100nm, the thickness of the Au plating layer is 50-140nm, and the total thickness of the Ti plating layer and the Au plating layer is not more than 150 nm.
6. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the thickness of the spin-coating negative photoresist in the step (7) is 1.5-3 μm.
7. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the thickness of the Ti plating layer in the step (8) is 10-100nm, the thickness of the Au plating layer is 200-900nm, and the total thickness of the Ti plating layer and the Au plating layer is 300-1000 nm.
8. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the thickness of the spin-coating positive photoresist in the step (10) is 1-3 μm.
9. The method for manufacturing the terahertz photoconductive antenna with the nano-electrodes as claimed in claim 1, wherein: the organic solvent used in the step is chlorobenzene or acetone.
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