CN107354513A - A kind of single germanium wafer etching process of efficient stable - Google Patents

A kind of single germanium wafer etching process of efficient stable Download PDF

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Publication number
CN107354513A
CN107354513A CN201710816709.2A CN201710816709A CN107354513A CN 107354513 A CN107354513 A CN 107354513A CN 201710816709 A CN201710816709 A CN 201710816709A CN 107354513 A CN107354513 A CN 107354513A
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Prior art keywords
germanium wafer
corrosive liquid
corrosion
etching process
efficient stable
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CN201710816709.2A
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CN107354513B (en
Inventor
吕菲
张伟才
常耀辉
王云彪
窦连水
刘洋
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CETC 46 Research Institute
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CETC 46 Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • C30B33/10—Etching in solutions or melts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/08—Germanium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Weting (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a kind of etching process that can corrode single germanium wafer with efficient stable.Single germanium wafer is immersed into NH4OH：H2O2：HF：DIW=1：2：3：In 5 corrosive liquid, the mass concentration of wherein hydrofluoric acid, hydrogen peroxide and ammonium hydroxide is respectively 40 ± 1%, 30 ± 1% and 25 ± 1%, stir, corrosive liquid temperature is maintained at 50 DEG C 53 DEG C, 10 single germanium wafers are immersed into corrosive liquid every time and rotate clockwise 3min20s ~ 3min40s, can remove 18 μm of thickness 16 μm.Corrosive liquid corrosion rate efficient stable in this etching process, and the fluctuation of corrosive liquid temperature, active ingredient is small, process conditions are easily controllable, and consistent uniform, the corrosion-free hole in germanium wafer surface after corrosion, quality is good, suitable for batch production.

Description

A kind of single germanium wafer etching process of efficient stable
Technical field
The invention belongs to semi-conducting material manufacture field, the single germanium wafer etching process of more particularly to a kind of efficient stable.
Background technology
Single germanium wafer is a kind of important semi-conducting material, is widely applied in infrared optical device, nuclear radiation detector, micro- The multiple fields such as electronic chip technology, Aero-Space solar cell substrate.Wet chemical etching technique is single germanium wafer chemical attack One of main method of processing, currently used H2O2/ HF etching process is widely used in single germanium wafer chemical attack processing One of method, having and remove germanium wafer surface damage layer, the effect such as release stress, its shortcoming is that temperature change is very fast in corrosion, Corrosion rate is unstable, and corrosive liquid composition transfer is very fast, is difficult to control in batch production process, the uniformity of product is poor. Therefore a kind of new etching process is invented, it is desirable to corrosive liquid temperature plateau, corrosion rate and solution composition are stable in course of reaction, The uniformity and stability of product are improved, while makes corrosion-free hole after germanium wafer corrosion, surface quality is very important well.
The content of the invention
In view of H2O2Problem present in/HF etching process, the present invention provide a kind of single germanium wafer corrosion work of efficient stable Skill, the corrosive liquid temperature plateau, corrosion rate and solution composition in the technique are stable, while surface quality is good after germanium wafer corrosion.
To achieve the above object, the present invention adopts the technical scheme that：A kind of single germanium wafer etching process of efficient stable, It is characterized in that：Single germanium wafer is immersed to the corrosive liquid being formulated by ammonium hydroxide, hydrogen peroxide, hydrofluoric acid and deionized water In corroded, etching time is 3min20s ~ 3min40s, and corrosion temperature is maintained at 50 DEG C ~ 53 DEG C；Hydrogen-oxygen in the corrosive liquid It is NH to change ammonium, hydrogen peroxide, hydrofluoric acid, the volume ratio of deionized water4OH：H2O2：HF：DIW=1：2：3：5.
The mass concentration of hydrofluoric acid, hydrogen peroxide and ammonium hydroxide in corrosive liquid of the present invention is respectively hydrofluoric acid 40 ± 1%, hydrogen peroxide 30 ± 1%, ammonium hydroxide 25 ± 1%.
The present invention has the advantage that is with beneficial effect：Hydrogenperoxide steam generator makees oxidant, and hydrofluoric acid is on the one hand as rotten Lose agent, on the other hand with ammonium hydroxide formed ammonium fluoride rise cushioning liquid, have stablizing solution pH value, reaction temperature and effectively into The effect divided, so as to stablize corrosion rate, the formation and expansion in control corrosion rate hole, germanium wafer surface quality is improved, improves and adds The high efficiency and stability of work.This method is easily operated, and theoretical principle is simple and reliable, chip process efficient stable, passes through The germanium wafer surface quality of corrosion meets late stage process requirement, and applied in actual production process, technological parameter is easily controlled, germanium wafer Surface uniformity, corrosion-free hole, there is certain practicality, suitable for batch production.
Embodiment
The invention will be further described with reference to embodiments：
Embodiment：Germanium wafer crystal orientation is P<100>, thickness is 420 μm, totally 60.Germanium wafer any surface finish not damaged before corrosion.
10 single germanium wafers are immersed what is be formulated by ammonium hydroxide, hydrogen peroxide, hydrofluoric acid and deionized water every time Corroded in corrosive liquid, rotated clockwise, etching time 3min30s, corrosion temperature be 50 DEG C beginning, after corrosion use from Scheming dries, and can remove 16 μm -18 μm of thickness.
Ammonium hydroxide, hydrogen peroxide, hydrofluoric acid, the volume ratio of deionized water are NH in corrosive liquid4OH：H2O2：HF：DIW= 1：2：3：5.Corrosive liquid stirs after the completion of preparing.The mass concentration of hydrofluoric acid in corrosive liquid is 40%；The matter of hydrogen peroxide It is 30% to measure concentration；The mass concentration of ammonium hydroxide is 25%.
The present embodiment have recorded the situation of change of corrosive liquid temperature in germanium wafer process, data such as table 1.
Table 1
Sequence number Per basket piece number Temperature DEG C before corrosion Temperature DEG C after corrosion Corrosion rate μm/min
1 10 50.4 52.0 5.39
2 10 50.8 52.4 5.41
3 10 50.2 51.8 5.38
4 10 50.6 52.4 5.42
5 10 50.8 52.6 5.39
6 10 50.4 52.2 5.40
Corrosive liquid temperature fluctuation is small as can be seen from Table 1, and corrosion rate is stable, suitable for batch production.Mesh after germanium wafer corrosion Examine and use metallography microscope sem observation surface quality, germanium wafer surface is uniform, corrosion-free hole, meets requirement.
Conclusion：Using this etching process corrosion rate efficient stable, corrosive liquid temperature and active ingredient fluctuation are small, while can To ensure single germanium wafer surface quality height, it is fully able to meet late stage process requirement.

Claims (2)

  1. A kind of 1. single germanium wafer etching process of efficient stable, it is characterised in that：Single germanium wafer is immersed by ammonium hydroxide, peroxide To change and corroded in the corrosive liquid that hydrogen, hydrofluoric acid and deionized water are formulated, etching time is 3min20s ~ 3min40s, Corrosion temperature is maintained at 50 DEG C ~ 53 DEG C；Ammonium hydroxide, hydrogen peroxide, hydrofluoric acid, the volume ratio of deionized water in the corrosive liquid For NH4OH：H2O2：HF：DIW=1：2：3：5.
  2. A kind of 2. single germanium wafer etching process of efficient stable according to claim 1, it is characterised in that：The corrosive liquid In hydrofluoric acid, the mass concentration of hydrogen peroxide and ammonium hydroxide be respectively hydrofluoric acid 40 ± 1%, hydrogen peroxide 30 ± 1%, hydrogen-oxygen Change ammonium 25 ± 1%.
CN201710816709.2A 2017-09-12 2017-09-12 High-efficiency stable germanium single crystal wafer etching process Active CN107354513B (en)

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CN107354513B CN107354513B (en) 2020-05-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110670141A (en) * 2019-11-13 2020-01-10 云南北方驰宏光电有限公司 Surface treatment device and method for high-purity germanium crystal material
CN114606505A (en) * 2022-03-24 2022-06-10 中锗科技有限公司 Shellac degumming agent for infrared germanium single crystal slicing and degumming method

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272748A (en) * 1964-06-29 1966-09-13 Western Electric Co Etching of silicon and germanium
JP2948414B2 (en) * 1991-06-12 1999-09-13 インターナショナル・ビジネス・マシーンズ・コーポレイション Method of depositing Ge on substrate and method of manufacturing semiconductor device
CN1363725A (en) * 2001-02-27 2002-08-14 南京大学 Selective chemical corrosion method to Si in Si/Ge structure
WO2004021420A3 (en) * 2002-08-29 2004-11-11 Massachusetts Inst Technology Fabrication method for a monocrystalline semiconductor layer on a substrate
US20080057678A1 (en) * 2006-08-31 2008-03-06 Kishor Purushottam Gadkaree Semiconductor on glass insulator made using improved hydrogen reduction process
US7709346B2 (en) * 2003-06-03 2010-05-04 Samsung Electronics Co., Ltd. Semiconductor device with trench gate type transistor and method of manufacturing the same
CN101701360A (en) * 2009-10-20 2010-05-05 南京中锗科技股份有限公司 Dislocation etching solution and etching method of (100) germanium monocrystal
CN104269347A (en) * 2014-09-10 2015-01-07 清华大学 Germanium film thinning method
CN104862702A (en) * 2015-05-21 2015-08-26 中国科学院半导体研究所 Etching solution for dislocation display of monocrystal germanium wafer deflecting to crystal orientation [111] and etching method
CN106567079A (en) * 2016-09-23 2017-04-19 中锗科技有限公司 Corrosive liquid for detecting dislocation of monocrystalline germanium slices and corrosion method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272748A (en) * 1964-06-29 1966-09-13 Western Electric Co Etching of silicon and germanium
JP2948414B2 (en) * 1991-06-12 1999-09-13 インターナショナル・ビジネス・マシーンズ・コーポレイション Method of depositing Ge on substrate and method of manufacturing semiconductor device
CN1363725A (en) * 2001-02-27 2002-08-14 南京大学 Selective chemical corrosion method to Si in Si/Ge structure
WO2004021420A3 (en) * 2002-08-29 2004-11-11 Massachusetts Inst Technology Fabrication method for a monocrystalline semiconductor layer on a substrate
US7709346B2 (en) * 2003-06-03 2010-05-04 Samsung Electronics Co., Ltd. Semiconductor device with trench gate type transistor and method of manufacturing the same
US20080057678A1 (en) * 2006-08-31 2008-03-06 Kishor Purushottam Gadkaree Semiconductor on glass insulator made using improved hydrogen reduction process
CN101701360A (en) * 2009-10-20 2010-05-05 南京中锗科技股份有限公司 Dislocation etching solution and etching method of (100) germanium monocrystal
CN104269347A (en) * 2014-09-10 2015-01-07 清华大学 Germanium film thinning method
CN104862702A (en) * 2015-05-21 2015-08-26 中国科学院半导体研究所 Etching solution for dislocation display of monocrystal germanium wafer deflecting to crystal orientation [111] and etching method
CN106567079A (en) * 2016-09-23 2017-04-19 中锗科技有限公司 Corrosive liquid for detecting dislocation of monocrystalline germanium slices and corrosion method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110670141A (en) * 2019-11-13 2020-01-10 云南北方驰宏光电有限公司 Surface treatment device and method for high-purity germanium crystal material
CN114606505A (en) * 2022-03-24 2022-06-10 中锗科技有限公司 Shellac degumming agent for infrared germanium single crystal slicing and degumming method

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