CN109581830A - A kind of method for stripping metal based on laser hot-die photoetching - Google Patents

A kind of method for stripping metal based on laser hot-die photoetching Download PDF

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Publication number
CN109581830A
CN109581830A CN201910052997.8A CN201910052997A CN109581830A CN 109581830 A CN109581830 A CN 109581830A CN 201910052997 A CN201910052997 A CN 201910052997A CN 109581830 A CN109581830 A CN 109581830A
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CN
China
Prior art keywords
aginsbte
layer
photoetching
die
system phase
Prior art date
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Pending
Application number
CN201910052997.8A
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Chinese (zh)
Inventor
王正伟
魏劲松
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Priority to CN201910052997.8A priority Critical patent/CN109581830A/en
Publication of CN109581830A publication Critical patent/CN109581830A/en
Pending legal-status Critical Current

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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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/428—Stripping or agents therefor using ultrasonic means only

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • ing And Chemical Polishing (AREA)
  • Surface Treatment Of Glass (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A kind of method for stripping metal based on laser hot-die photoetching, based on laser hot-die photoetching principle, by laser beam, direct write exposes on sulphur system phase change film material, micro-nano graphic structure is formed using selective etching of the ammonium sulfide etchant solution to phase-change material, sulphur removal system phase change film material is removed in ammonium ceric nitrate and nitric acid mixed solution after plating one layer of chromium metallic film on forming micro-nano structure using magnetron sputtering technique, upper layer layers of chrome is removed under ultrasonication, finally forms chromium graph layer in quartz glass on piece.The present invention can be achieved to inscribe less than light class size and greater than the arbitrary dimension of light class size, successfully will can be transferred to chrome thin film layer in the micro-nano structure complementation of sulphur system phase-change thin film.

Description

A kind of method for stripping metal based on laser hot-die photoetching
Technical field
The present invention relates to a kind of micro-nano graph layers to shift field, especially a kind of metal-stripping based on laser hot-die photoetching Method.
Background technique
In microelectromechanical systems and integrated circuit processing technique, realize that pattern transfer is a step critical process, wherein In order to form metal pattern, metal lift-off material is generally used, i.e., forms micro-nano pattern on a photoresist using photoetching technique, so Metal deposit is carried out above afterwards, then photoresist is removed, forms metal pattern.Most representative is the binary such as lithography mask version The preparation of optical element is that complicated geometric figure is formed on the glass substrate containing metallic film, in the manufacture of semiconductor In the process, circuit structure can be formed on a silicon substrate using photomask board and the means of exposure；Mask plate is mainly by substrate It is formed with light-proof material, substrate is usually high-purity, antiradar reflectivity, low-expansion quartz glass, and light non-transmittable layers are main By the layers of chrome for being plated in quartz glass plate through sputtering method.
Metal lift-off material step mainly includes the techniques such as figure generation, development, deposited metal, removing, detection；In figure It during generation, is mainly exposed on a photoresist using technologies such as electron beam lithography, laser direct-writings, without there is no inscribe speed Slowly, the problems such as exposure area is small, and equipment is expensive, complicated for operation；The photoetching of laser hot-die is as a kind of novel photoetching technique, tool There is the advantages that easy to operate, characteristic size is small, across scale inscription, and inscription speed is fast, there is irreplaceable work in field of lithography With metal lift-off material will be applied to well.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, provide a kind of based on laser hot-die photoetching Method for stripping metal.
In order to achieve the above objectives, technical solution of the invention is as follows:
A kind of method for stripping metal based on laser hot-die photoetching, comprising the following steps:
A) one layer of AgInSbTe sulphur system phase change material film is plated using magnetron sputtering technique in quartz glass substrate on piece；
B) wavelength is used to carry out for the laser beam of 405nm to the quartz glass substrate for being coated with AgInSbTe sulphur system phase-change thin film Laser direct-writing exposure；
C) selective wet etching is carried out to the film after laser explosure effect using developer solution, being formed has micro-nano graph The AgInSbTe graph layer of structure uses atomic force microscope structural characterization micro-nano graphic structure height for D；
D) magnetron sputtering technique is used to plate a layer thickness as the chromium of d (d < D) on AgInSbTe graph layer described above Layer metallic film；
E) under ultrasonication, AgInSbTe sulphur system phase-change material is removed using corrosive liquid, removes AgInSbTe sulphur system phase Become material upper layer chromium metal layer, retains the chromium metal film layer directly contacted with quartz glass plate；
F) quartz glass obtained above for being loaded with chromium graph layer is immersed in corrosive liquid described in step e), temperature 15 DEG C -25 DEG C, time 5-15min, removal residual AgInSbTe sulphur system phase-change material is cleaned, elevated pressure nitrogen air-blowing using deionized water It does to get chromium graph layer is arrived.
Further, in the step c), wet etching is specifically that the AgInSbTe sulphur system phase-change material is thin Film is placed in developer solution, and 15 DEG C -25 DEG C of temperature, time 5-10min.
Further, in the step c), the developer solution is ammonium sulfide solution (concentration 15%-25%)；
Further, in the step d), the corrosive liquid is that ammonium ceric nitrate (concentration 10%-20%) and nitric acid are (dense Spend 5%-10%) 4:1 mixed aqueous solution, 15 DEG C -25 DEG C of temperature, time 5-10sec.
Compared with prior art, technical effect of the invention is as follows:
1) use AgInSbTe sulphur system's phase change film material as photoresist, since the hot threshold value of material and thermal diffusion are imitated Fruit, and successfully will be in the micro- of AgInSbTe film, it can be achieved that be less than light class size and inscribe greater than the arbitrary dimension of light class size Micro-nano structure complementation is transferred to chrome thin film layer, that is, forms lithography mask version；
2) laser hot-die photoetching technique is used, it is easy to operate.
Detailed description of the invention
The present invention is based on the method for stripping metal flow diagrams of laser hot-die photoetching by Fig. 1；
The present invention is based on the AgInSbTe graph layers of the method for stripping metal of laser hot-die photoetching by Fig. 2；
The present invention is based on the chromium graph layers of the method for stripping metal of laser hot-die photoetching by Fig. 3；
In figure: 1-AgInSbTe film, 2- quartz glass substrate, 3- layers of chrome metallic film.
Specific embodiment
Below by embodiment and attached drawing, the invention will be further described, but protection model of the invention should not be limited with this It encloses.
As shown in Figure 1, a kind of method for stripping metal based on laser hot-die photoetching comprising steps of
A) one layer of AgInSbTe sulphur system phase change material film 1 is plated using magnetron sputtering technique on quartz glass substrate 2；
B) wavelength is used to carry out for the laser beam of 405nm to the quartz glass substrate for being coated with AgInSbTe sulphur system phase-change thin film Laser direct-writing exposure, laser action are partially converted into crystalline state, and the non-effect partial of laser keeps deposited；
C) using concentration is the ammonium sulfide developer solution of 15%-25% to the AgInSbTe sulphur system after the effect of above-mentioned laser explosure Phase change material film carries out selective wet etching, and development temperature is 15 DEG C -25 DEG C, and developing time 5-10min, formation has The AgInSbTe graph layer of micro-nano graphic structure uses atomic force microscope structural characterization micro-nano graphic structure height for 90nm, As shown in Figure 2；
D) chromium for using magnetron sputtering technique to plate a layer thickness as 85nm on the AgInSbTe graph layer after above-mentioned development Layer metallic film 3；
E) under ultrasonication, use mass fraction for the 4:1 of the ammonium ceric nitrate of 10%-20% and the nitric acid of 5%-15% Mixed solution removes AgInSbTe sulphur system phase-change material, removes AgInSbTe sulphur system's phase-change material upper layer chromium metal layer, corrosion temperature 15 DEG C -25 DEG C, time 5-10sec of degree retains the chromium metal film layer that directly contact with quartz glass plate to get chromium figure is arrived Layer；
F) quartz glass obtained above for being loaded with chromium graph layer is immersed in the ammonium sulfide that step mass fraction is 17% In developer solution, 15 DEG C -25 DEG C of temperature, time 5-15min, removal residual AgInSbTe sulphur system phase-change material uses deionization afterwards Water cleaning, high pressure nitrogen drying obtains chromium metal pattern layer, as shown in figure 3, height is 80nm.

Claims (4)

1. a kind of method for stripping metal based on laser hot-die photoetching, it is characterised in that method includes the following steps:
A) one layer of AgInSbTe sulphur system phase change material film is plated using magnetron sputtering technique in quartz glass substrate on piece；
B) wavelength is used to carry out laser to the quartz glass substrate for being coated with AgInSbTe sulphur system phase-change thin film for the laser beam of 405nm Direct write exposure；
C) selective wet etching is carried out to the film after laser explosure using developer solution, being formed has micro-nano graphic structure AgInSbTe graph layer uses atomic force microscope structural characterization micro-nano graphic structure height for D；
D) the layers of chrome metallic film for using magnetron sputtering technique to plate a layer thickness as d on the AgInSbTe graph layer, Middle d < D；
E) under ultrasonication, AgInSbTe sulphur system phase-change material is removed with corrosive liquid, removes AgInSbTe sulphur system phase-change material The chromium metallic film on upper layer retains the chromium metal film layer directly contacted with quartz glass plate, obtains chromium graph layer；
F) quartz glass for being loaded with chromium graph layer for obtaining step e) is immersed in developer solution described in step c), temperature 15 DEG C -25 DEG C, time 5-15min, removal residual AgInSbTe sulphur system phase-change material.
2. the method for stripping metal according to claim 1 based on laser hot-die photoetching, it is characterised in that the step C) in, wet etching is specifically that the AgInSbTe sulphur system phase change material film is placed in developer solution, and 15 DEG C -25 of temperature DEG C, time 5-10min.
3. the method for stripping metal according to claim 2 based on laser hot-die photoetching, which is characterized in that step c) is described Developer solution be ammonium sulfide solution, concentration 17%.
4. the method for stripping metal according to claim 1 based on laser hot-die photoetching, which is characterized in that step e) is described Corrosive liquid be ammonium ceric nitrate (concentration 10%-20%) and nitric acid (concentration 5%-10%) 4:1 mixed aqueous solution, temperature 15 DEG C -25 DEG C, time 5-10sec.
CN201910052997.8A 2019-01-21 2019-01-21 A kind of method for stripping metal based on laser hot-die photoetching Pending CN109581830A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111580357A (en) * 2020-01-02 2020-08-25 中国科学院上海光学精密机械研究所 Developing solution for laser thermal mold photoresist and preparation method thereof
CN112007592A (en) * 2020-09-03 2020-12-01 中科芯云微电子科技有限公司 Acid colloid for eliminating photoetching layout and protecting intellectual property of integrated circuit and application thereof
CN112309839A (en) * 2020-10-16 2021-02-02 中国科学院上海光学精密机械研究所 Preparation method of silicon oxide graph structure based on hot mold photoetching

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1397986A (en) * 2001-07-23 2003-02-19 北京大学 Method for stripping metal
CN101419400A (en) * 2007-10-24 2009-04-29 中国科学院微电子研究所 Method for dry etching through metal chromium masking film
CN108376642A (en) * 2018-02-02 2018-08-07 中国科学院上海光学精密机械研究所 Ge2Sb2Te5The dual-purpose wet etching method of the positive negtive photoresist of sulphur system phase change film material
CN108563099A (en) * 2018-01-18 2018-09-21 中国科学院上海光学精密机械研究所 A kind of nano-imprint stamp preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1397986A (en) * 2001-07-23 2003-02-19 北京大学 Method for stripping metal
CN101419400A (en) * 2007-10-24 2009-04-29 中国科学院微电子研究所 Method for dry etching through metal chromium masking film
CN108563099A (en) * 2018-01-18 2018-09-21 中国科学院上海光学精密机械研究所 A kind of nano-imprint stamp preparation method
CN108376642A (en) * 2018-02-02 2018-08-07 中国科学院上海光学精密机械研究所 Ge2Sb2Te5The dual-purpose wet etching method of the positive negtive photoresist of sulphur system phase change film material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111580357A (en) * 2020-01-02 2020-08-25 中国科学院上海光学精密机械研究所 Developing solution for laser thermal mold photoresist and preparation method thereof
CN112007592A (en) * 2020-09-03 2020-12-01 中科芯云微电子科技有限公司 Acid colloid for eliminating photoetching layout and protecting intellectual property of integrated circuit and application thereof
CN112309839A (en) * 2020-10-16 2021-02-02 中国科学院上海光学精密机械研究所 Preparation method of silicon oxide graph structure based on hot mold photoetching

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Application publication date: 20190405

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