CN107154331A - Method for Anisotropic Etching of Vanadium Oxide - Google Patents
Method for Anisotropic Etching of Vanadium Oxide Download PDFInfo
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- CN107154331A CN107154331A CN201710334171.1A CN201710334171A CN107154331A CN 107154331 A CN107154331 A CN 107154331A CN 201710334171 A CN201710334171 A CN 201710334171A CN 107154331 A CN107154331 A CN 107154331A
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- 238000005530 etching Methods 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 67
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 title abstract description 3
- 238000001020 plasma etching Methods 0.000 claims abstract description 48
- 238000009832 plasma treatment Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 75
- 229910052720 vanadium Inorganic materials 0.000 claims description 43
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 43
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 229910015844 BCl3 Inorganic materials 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000003628 erosive effect Effects 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/30—Electron-beam or ion-beam tubes for localised treatment of objects
- H01J37/305—Electron-beam or ion-beam tubes for localised treatment of objects for casting, melting, evaporating, or etching
- H01J37/3053—Electron-beam or ion-beam tubes for localised treatment of objects for casting, melting, evaporating, or etching for evaporating or etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/021—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient formed as one or more layers or coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/026—Vanadium oxides or oxidic compounds, e.g. VOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/041—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient formed as one or more layers or coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
- H01C7/043—Oxides or oxidic compounds
- H01C7/047—Vanadium oxides or oxidic compounds, e.g. VOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/30—Electron or ion beam tubes for processing objects
- H01J2237/31—Processing objects on a macro-scale
- H01J2237/3151—Etching
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Ceramic Engineering (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Drying Of Semiconductors (AREA)
Abstract
The invention provides a method for anisotropic etching of vanadium oxide. The method comprises the following steps: s1, using Cl-based gas pair VxOyCarrying out first plasma etching on the layer, and introducing O in the etching process2And Ar; s2, etching V after the first plasma by using the post-processing gas including at least one of N2, H2 and ArxOyThe layer is subjected to a plasma treatment. Because the boiling point of the chloride is higher than that of the fluoride, partial chlorination products can be deposited on the side wall to protect the side wall from being further etched transversely, and introduced Ar ions can sputter partial VxOyThe material is reversely deposited on the side wall to play a role in protection; and, since Cl-based gas is apt to be H in the air2And acidic substances generated by the action of O, so that the acidic substances adsorbed on the etched surface can be removed or neutral substances can be generated through the plasma treatment, and the corrosion phenomenon after the etched surface is further effectively avoided.
Description
Technical field
The present invention relates to dry etching technology field, etched in particular to a kind of anisotropic oxide of vanadium
Method.
Background technology
The oxide of vanadium due to higher TCR (thermo-sensitive resistor coefficient), so as to as temperature sensing material heat into
The fields such as picture have a wide range of applications.
The oxide valence state of vanadium is relatively more, the barium oxide actually grown with the mode of reactive sputtering be often VO,
V2O3、VO2And V2O5The mixture coexisted, therefore, generally uses VxOyTo represent.
In actual applications it is generally necessary to VxOyAnisotropic etching is carried out, to realize the essence to its pattern and size
Really processing, anisotropic dry is realized as disclosed in the prior art using carbon fluorine base gas and oxygen under normal temperature (20 DEG C)
Etch VO2.However, above-mentioned technology can not the normal vanadium of other valence states of anisotropic etching oxide, easily produce lateral bore
Lose phenomenon.
The content of the invention
It is a primary object of the present invention to provide the method that a kind of anisotropic oxide of vanadium is etched, to solve existing skill
The problem of anisotropic dry etch in art easily produces lateral undercut when etching the oxide of vanadium of various valence states.
To achieve these goals, according to an aspect of the invention, there is provided a kind of anisotropic oxide of vanadium is carved
The method of erosion, comprises the following steps：S1, using Cl base gases to VxOyLayer carries out the first plasma etching, and in the mistake of etching
O is passed through in journey2And Ar；S2, using the post-treatment gas including at least one of N2, H2 and Ar to the first plasma etching after
VxOyLayer carries out plasma treatment.
Further, in step sl, Cl bases gas, the O of use2Flowrate proportioning with Ar is 1~3:1~3:1~3,
It is preferred that the flow of Cl base gases is 5~100sccm, O2Flow be 20~200sccm, Ar flow is 50~100sccm.
Further, the first plasma etching etches for inductive coupled plasma.
Further, in step sl, the gas pressure intensity of the first plasma etching is 3~60mT, Top electrode radio frequency work(
Rate is 100~500W, and bottom electrode radio-frequency power is 30~200W.
Further, in step sl, the etching temperature of the first plasma etching is 20~100 DEG C.
Further, in step s 2, using N2、O2、H2With Ar to the V after the first plasma etchingxOyLayer progress etc.
Ion processing, preferably N2、O2、H2Flowrate proportioning with Ar is 1~3:1~3:1~3:1~3, more preferably N2Flow for 10~
100sccm, O2Flow be 10~100sccm, H2Flow be 5~50sccm, Ar flow is 10~100sccm.
Further, in step s 2, the gas pressure intensity of plasma treatment is 3~60mT, and Top electrode radio-frequency power is
100W~800W, bottom electrode radio-frequency power is 0~100W.
Further, Cl bases gas is selected from Cl2, HCl and BCl3Any of or it is a variety of.
Further, V is formedxOyThe material of layer is selected from VO, V2O3、VO2And V2O5Any of or it is a variety of.
Further, before step S1, method is further comprising the steps of：Offer is provided with VxOyThe substrate of layer, in VxOy
The surface of layer sets mask layer and mask layer is performed etching, and makes part VxOyLayer is exposed.
Further, mask layer is silicon nitride layer, it is preferred to use carbon fluorine base gas carries out the second plasma to mask layer
Etching, and it is passed through O during the second plasma etching2。
Apply the technical scheme of the present invention there is provided a kind of method that oxide to vanadium carries out anisotropic etching, should
First using Cl base gases to V in methodxOyLayer carries out plasma etching, and is passed through during etching O2And Ar, due to vanadium
Chloride boiling point it is high with respect to fluoride so that partial oxidation product can be deposited on side wall protective side wall and be not continued transverse direction
Undercutting, Ar ions can sputter part VxOyThe anti-side wall that is deposited on of material plays a protective role, and then not only realizes to VxOyWell
Anisotropic etching result, and above-mentioned VxOyIt can cover from the insensitive pure vanadium of valence state of oxidation to V2O5Highest valence state
Various valence states vanadium oxide；Then using again includes N2、H2With at least one of Ar post-treatment gas to the first grade from
V after daughter etchingxOyLayer carries out plasma treatment, is easy to the H in air due to Cl base gases2The acid that O is acted on and produced
Matter, so as to can be removed the acidic materials for being adsorbed in etching surface or generation neutral substance by above-mentioned plasma treatment, enters
One step efficiently avoid the generation of etching surface post-etching phenomenon.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The Figure of description for constituting the part of the present invention is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the method that a kind of oxide to vanadium that embodiment of the present invention is provided carries out anisotropic etching
Schematic flow sheet；
Fig. 2 is shown in comparative example 1 carries out the SEM figures after anisotropic etching to the oxide of vanadium；
Fig. 3 is shown in embodiment 1 carries out the SEM figures after anisotropic etching to the oxide of vanadium；And
Fig. 4 is shown in embodiment 7 carries out the SEM figures after anisotropic etching to the oxide of vanadium.
Embodiment
It should be noted that in the case where not conflicting, the embodiment in the present invention and the feature in embodiment can phases
Mutually combination.Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
In order that those skilled in the art more fully understand the present invention program, below in conjunction with the embodiment of the present invention
Accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill people
The every other embodiment that member is obtained under the premise of creative work is not made, should all belong to the model that the present invention is protected
Enclose.
It should be noted that term " first " in description and claims of this specification and above-mentioned accompanying drawing, "
Two " etc. be for distinguishing similar object, without for describing specific order or precedence.It should be appreciated that so using
Data can exchange in the appropriate case, so as to embodiments of the invention described herein.In addition, term " comprising " and " tool
Have " and their any deformation, it is intended that covering is non-exclusive to be included, for example, containing series of steps or unit
Process, method, system, product or equipment are not necessarily limited to those steps clearly listed or unit, but may include without clear
It is listing to Chu or for the intrinsic other steps of these processes, method, product or equipment or unit.
As described by background technology, in the prior art to normally anisotropic etching VO can not be removed2Outside other
The oxide of the vanadium of valence state, easily produces lateral undercut.In order to solve the above problems, the invention provides a kind of oxygen of vanadium
The method of compound anisotropic etching, as shown in figure 1, comprising the following steps：S1, using Cl base gases to VxOyLayer carries out first
Plasma etching, and it is passed through during etching O2And Ar；S2, using the rear place including at least one of N2, H2 and Ar
Process gases is to the V after the first plasma etchingxOyLayer carries out plasma treatment.
In the method that the anisotropic oxide of above-mentioned vanadium provided by the present invention is etched, first using Cl base gases pair
VxOyLayer carries out plasma etching, and is passed through during etching O2And Ar, then using again includes N2、H2With in Ar at least
A kind of post-treatment gas is to the V after the first plasma etchingxOyLayer carries out plasma treatment, because chloride boiling point is relative
Fluoride is high, so that partial oxidation product can be deposited on side wall protective side wall and be not continued horizontal undercutting, and the Ar introduced
Ion can sputter part VxOyThe anti-side wall that is deposited on of material plays a protective role, and then not only realizes to VxOyIt is good it is each to
Anisotropic etch result, and above-mentioned VxOyIt can cover from the insensitive pure vanadium of valence state of oxidation to V2O5Highest valence state it is various
The oxide of the vanadium of valence state；Also, it is easy to the H in air due to Cl base gases2The acidic materials that O is acted on and produced, so that logical
The acidic materials for being adsorbed in etching surface can be removed or generation neutral substance by crossing above-mentioned plasma treatment, effectively further
Avoid the generation of etching surface post-etching phenomenon.
The example of the method for the anisotropic oxide etching of the vanadium provided according to the present invention is provided
Property embodiment.However, these illustrative embodiments can be implemented by many different forms, and it should not be explained
To be only limited to embodiments set forth herein.It should be appreciated that thesing embodiments are provided so that the application's
It is open thoroughly and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
First, step S1 is performed：Using Cl base gases to VxOyLayer carries out the first plasma etching, and in the mistake of etching
O is passed through in journey2And Ar.In the prior art it has been generally acknowledged that the chloride fusing point of vanadium is high and is not easy to plasma etching, and in this hair
In bright above-mentioned steps S1, because by chloride boiling point, with respect to fluoride height, (VF5 boiling points are only 19.5 under such as normal pressure
DEG C, and VCl3 boiling point is up to 250 DEG C), partial oxidation product is deposited on side wall protective side wall and be not continued horizontal undercutting,
And the Ar ions introduced can sputter part VxOyThe anti-side wall that is deposited on of material plays a protective role, and then not only realizes to VxOy
Good anisotropic etching result, and above-mentioned VxOyIt can cover from the insensitive pure vanadium of valence state of oxidation to V2O5Highest
The oxide of the vanadium of the various valence states of valence state.
Cl base gases are being used to VxOyDuring layer carries out the first plasma etching, etch period can basis
VxOyThe thickness and the etching gas flow that is passed through of layer is set, and in order to which the anisotropy for improving plasma etching technique is carved
Effect is lost, makes the surface after etching more smooth, it is preferable that Cl bases gas, the O of use2Flowrate proportioning with Ar is 1~3:1
~3:1~3.
In a preferred embodiment, the flow of above-mentioned Cl bases gas is 5~100sccm, above-mentioned O2Flow be
20~200sccm, above-mentioned Ar flow are 50~100sccm；It is further preferable that the flow of above-mentioned Cl bases gas be 20~
100sccm.By the flow restriction of each gas that will be passed through in plasma etching technique in above-mentioned preferred parameter area, energy
Enough anisotropic etching effects for further improving plasma etching technique, so that the surface after etching is more smooth.
In a preferred embodiment, using Cl base gases to VxOyLayer carries out inductive coupled plasma etching
(ICP etchings).ICP etchings are due to using two independent radio frequency sources, so as to realize higher etching speed and relatively low
Etching injury, and the work gas of ICP etchings forces down, plasma density is high, so as to be conducive to controlling the pattern of etching surface.
It is above-mentioned preferred embodiment in, those skilled in the art can be according to prior art in ICP etching technics
Process conditions carry out reasonable set, in order to improve the anisotropic etching effect of plasma etching technique, it is further preferable that
To VxOyLayer carry out the first plasma etching during, gas pressure intensity be 3~60mT, Top electrode radio-frequency power be 100~
500W, bottom electrode radio-frequency power is 30~200W.Gas pressure intensity during above-mentioned plasma etching is far below atmospheric pressure
Lower progress, so as to make the byproduct fraction of generation volatilize.
In the prior art in order to realize to VO2Anisotropic dry etch, not only need use carbon fluorine base gas and oxygen
Gas is as etching gas, due to VO2With higher TCR (thermo-sensitive resistor coefficient), therefore also need to be maintained at etching temperature
Under normal temperature (20 DEG C), to ensure VO2Stability.And in the above method of the present invention, using Cl base gases to VxOyLayer is carried out
The etching temperature of first plasma etching can be 20~100 DEG C.Use the anisotropic dry etch side in the application
Method can realize VxOyEtching effect under large temperature range.
Cl base gases are being used to VxOyDuring layer carries out the first plasma etching, in order to realize to VxOyLayer is good
Good anisotropic etching result, Cl bases gas can be selected from Cl2, HCl and BCl3Any of or it is a variety of, and form above-mentioned
VxOyThe material of layer can be selected from VO, V2O3、VO2And V2O5Any of or it is a variety of.It can be realized using Cl bases gas
The anisotropic etching result good to the oxide of the vanadium of various valence states.
Before above-mentioned steps S1, the method for the anisotropic oxide etching of above-mentioned vanadium of the invention can also include with
Lower step：Offer is provided with VxOyThe substrate of layer, in VxOyThe surface of layer sets mask layer and mask layer is performed etching, and makes portion
Divide VxOyLayer is exposed.Above-mentioned mask layer is by photoetching process and etching technics with VxOyLayer surface formation has pierced pattern
Mask plate, so as to need the part V being etched awayxOyLayer is exposed, so as to use Cl bases gas to exposed VxOyLayer carries out the
During one plasma etching, the V that needs can be etched awayxOyMaterial is removed.
In VxOyDuring the surface of layer sets mask layer and mask layer is performed etching, it is preferable that in VxOyThe table of layer
The mask layer that face is set is silicon nitride layer；Also, it is further preferable that the second plasma is carried out to mask layer using carbon fluorine base gas
Body is etched, and is passed through O during above-mentioned second plasma etching2.Being adopted as silicon nitride layer can make as mask layer
For common insulation and passivation layer, while be infrared absorbing material again, so as to by the heat transfer of absorption to VxOyAnd utilization should
The resistance temperature-sensing property of material changes its resistance value, so the silicon nitride material after etching be able to will be retained as structure sheaf
Get off；Also, the anisotropy good to mask layer can be realized as etching gas using above-mentioned carbon fluorine base gas and oxygen
Result is etched, above-mentioned carbon fluorine base gas can be CF4 gases.
After above-mentioned steps S1 is completed, step S2 is performed：Using including N2、H2With at least one of Ar post processing gas
Body is to the V after the first plasma etchingxOyLayer carries out plasma treatment.Easily exist because Cl base gases are readily adsorbed in chip
With the H in air during sample exposure air2O effects produce acidic materials corrosion VxOy, so that be easily caused etching after sample big
Post-etching (corrosion) phenomenon is produced in gas, and the present invention includes N by being used in etching (before going out vacuum cavity) in situ2、
H2Post-treatment gas with least one of Ar is to the V after the first plasma etchingxOyLayer carries out plasma treatment, so as to
With H in air during enough by Cl bases gas exposed to air2The acidic materials that O is acted on and produced are removed or generation neutral substance.
V after to the first plasma etchingxOyDuring layer carries out plasma treatment, etch period can basis
The flow of the post-treatment gas being passed through is set, and in order to improve treatment effect of the plasma treatment process to etching surface, with
Realize to VxOyGood anisotropic etching result, can use N2、O2、H2The first plasma is carved with Ar mixed gas
V after erosionxOyLayer carries out plasma treatment, above-mentioned N2And H2It can be reacted with the acidic materials of etching surface, to generate neutrals
Matter, above-mentioned Ar can play a part of bombarding etching surface impurity, and above-mentioned O2For the photoresist remained with etching surface
Deng impurity reaction, so as to realize effective removal to etching surface impurity jointly.
In a preferred embodiment, N in above-mentioned post-treatment gas2、O2、H2Flowrate proportioning with Ar is 1~3:1
~3:1~3, it is further preferable that above-mentioned N2Flow be 10~100sccm, above-mentioned O2Flow be 10~100sccm, above-mentioned H2
Flow be 5~50sccm, and above-mentioned Ar flow be 10~100sccm.By each by what is be passed through in plasma etching technique
The flow restriction of gas can be improved further to V in above-mentioned preferred parameter areaxOyGood anisotropic etching knot
Really, so that the surface after etching is more smooth.
In above-mentioned steps S2, the process conditions that those skilled in the art can also be handled according to prior art article on plasma
Reasonable set is carried out, in order to improve the post processing effect of plasma treatment process, it is preferable that the gas pressure of above-mentioned plasma treatment
It is 3~60mT by force, Top electrode radio-frequency power is 100W~800W, and bottom electrode radio-frequency power is 0~100W.
The method that the anisotropic oxide etching for the vanadium that the present invention is provided is further illustrated below in conjunction with embodiment.
Embodiment 1
The method of the anisotropic oxide etching for the vanadium that the present embodiment is provided comprises the following steps：
There is provided be provided with V by S1xOyThe substrate of layer, in VxOyThe surface of layer sets SiN mask layers, wherein, form VxOyLayer
Material is by VO, V2O3、VO2And V2O5The mixture of composition；
S2, coats photoresist (PR) on the surface of mask layer and graphical, using CF4 gases to covering using photoetching process
The mask layer for having photoresist carries out reactive ion etching, and is passed through during etching O2, by etching so as to not be photo-etched
The part V of glue coveringxOyLayer is exposed；
S3, using Cl2To exposed V at 20 DEG CxOyLayer carries out reactive ion etching (RIE etchings), and in the mistake of etching
O is passed through in journey2And Ar, Cl2Flow be 4sccm, O2Flow 15sccm, and Ar flow be 45sccm, and etching process in
Gas pressure intensity 2mT is kept, radio-frequency power is 90W, and the time is 10s；
S4, using including N2, H2 and Ar to the V after the first plasma etchingxOyLayer carries out plasma treatment, N2Stream
Measure as 8sccm, H flows are 4sccm, and Ar is 8sccm.Gas pressure intensity 2mT is kept in plasma treatment process, upper radio-frequency power is
90W, lower radio-frequency power is 50W, and the time is 10s.
Embodiment 2
The difference of the method and embodiment 1 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using Cl2To exposed VxOyLayer progress inductive coupled plasma etching (ICP etchings), and
O is passed through during etching2And Ar, Cl2Flow be 60sccm, O2Flow 50sccm, and Ar flow be 10sccm, and
It is 20mT that gas pressure intensity is kept in etching process, and Top electrode radio-frequency power is 95W, and bottom electrode radio-frequency power is 25W.
In step s 4, it is passed through N2, O2, H2And Ar, N2Flow is 5sccm, O2Flow is 10sccm, H2Flow is 5sccm,
Ar is 10sccm.Gas pressure intensity 3mT is kept in plasma process, upper radio-frequency power is 450W, and lower radio-frequency power is 50W, time
For 10s.
Embodiment 3
The difference of the method and embodiment 2 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, Cl2Flow 5sccm, O2Flow be 20ccm, and Ar flow be 50sccm, keep etching
During gas pressure intensity be 3mT, Top electrode radio-frequency power be 100W, bottom electrode radio-frequency power be 30W.
Embodiment 4
The difference of the method and embodiment 2 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, Cl2Flow 100sccm, O2Flow 200sccm, and Ar flow 100sccm, keep etching
During gas pressure intensity be 60mT, Top electrode radio-frequency power be 500W, bottom electrode radio-frequency power be 200W.
Embodiment 5
The difference of the method and embodiment 4 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s 4, N2Flow is 10sccm, O2Flow is 10sccm, H2Flow is 5sccm, and Ar is 10sccm.Deng from
Gas pressure intensity 3mT is kept in subprocess, upper radio-frequency power is 100W.
Embodiment 6
The difference of the method and embodiment 5 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s 4, N2Flow is 10sccm, O2Flow is 10sccm, H2Flow is 5sccm, and Ar is 10sccm, wait from
Gas pressure intensity 60mT is kept in subprocess, upper radio-frequency power is 800W, and lower radio-frequency power is 100W.
Embodiment 7
The difference of the method and embodiment 6 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, Cl2Flow 62sccm, O2Flow be 105sccm, and Ar flow be 75sccm, and keep
Gas pressure intensity in etching process is 30mT, and Top electrode radio-frequency power is 250W, and bottom electrode radio-frequency power is 150W；
In step s 4, N2Flow is 50sccm, O2Flow is 50sccm, H2Flow is 25sccm, and Ar is 25sccm.Deng
Gas pressure intensity 50mT is kept during ion, upper radio-frequency power is 450W, and lower radio-frequency power is 50W, and the time is 10s.
Embodiment 8
The difference of the method and embodiment 7 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using HCl gases to exposed VxOyLayer carries out ICP etchings.
Embodiment 9
The difference of the method and embodiment 7 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using BCl3Gas is to exposed VxOyLayer carries out ICP etchings.
Embodiment 10
The difference of the method and embodiment 7 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using Cl2To exposed V at 50 DEG CxOyLayer carries out ICP etchings.
Embodiment 11
The difference of the method and embodiment 7 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using Cl2To exposed V at 100 DEG CxOyLayer carries out ICP etchings.
Comparative example 1
The difference of the method and embodiment 1 of the anisotropic oxide etching for the vanadium that the present embodiment is provided is：
In step s3, using CHF3Gas is to exposed VxOyReactive ion etching is carried out, and is led to during etching
Enter O2, CHF3Flow 60sccm, O2Flow be to keep gas pressure intensity to be 50mT, radio-frequency power in 50sccm, and etching process
For 500W.
Plasma etch process in above-described embodiment 1 to 11 and comparative example 1 is entered in Lam 9400DFM etching machines
OK, pattern of the oxide of vanadium in above-described embodiment and comparative example after anisotropic etching is observed using SEM, from test knot
Fruit can be seen that the V in comparative example 1xOyLayer anisotropy after being etched is poor, produces lateral undercut, as shown in Figure 2；
And the V in embodiment 1 to 11xOyLayer in the rear side that is etched to not producing particularly apparent undercut, it is and more smooth,
From embodiment 10 and 11 it can also be seen that V can be realized using the anisotropic etch process of the applicationxOyIn larger temperature model
Etching effect under enclosing, wherein, the SEM figures of embodiment 1 are as shown in figure 3, the SEM figures of embodiment 7 are as shown in Figure 4.
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
1st, using Cl base gases to VxOyLayer carries out plasma etching, and is passed through during etching O2And Ar, due to
The chloride boiling point of vanadium is high with respect to fluoride, so that partial oxidation product can be deposited on side wall protective side wall and be not continued horizontal stroke
To undercutting, Ar ions can sputter part VxOyThe anti-side wall that is deposited on of material plays a protective role, and then not only realizes to VxOyIt is good
Good anisotropic etching result, and above-mentioned VxOyIt can cover from the insensitive pure vanadium of valence state of oxidation to V2O5Highest price
The oxide of the vanadium of the various valence states of state；
2nd, using including N2、H2Post-treatment gas with least one of Ar is to the V after the first plasma etchingxOyLayer
Plasma treatment is carried out, is easy to the H in air due to Cl base gases2The acidic materials that O is acted on and produced, so that by above-mentioned etc.
Ion processing can remove the acidic materials for being adsorbed in etching surface or generation neutral substance, effectively further avoid quarter
Lose the generation of surface post-etching phenomenon.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (11)
1. the method for the anisotropic oxide etching of a kind of vanadium, it is characterised in that comprise the following steps：
S1, using Cl base gases to VxOyLayer carries out the first plasma etching, and is passed through during etching O2And Ar；
S2, using including N2、H2Post-treatment gas with least one of Ar is to the V after the first plasma etchingxOyLayer
Carry out plasma treatment.
2. according to the method described in claim 1, it is characterised in that in the step S1, the Cl bases gas of use, institute
State O2Flowrate proportioning with the Ar is 1~3:1~3:1~3, the flow of preferably described Cl bases gas is 5~100sccm, institute
State O2Flow be 20~200sccm, the flow of the Ar is 50~100sccm.
3. method according to claim 1 or 2, it is characterised in that first plasma etching is inductive coupled etc.
Plasma etching.
4. method according to claim 3, it is characterised in that in the step S1, first plasma etching
Gas pressure intensity be 3~60mT, Top electrode radio-frequency power be 100~500W, bottom electrode radio-frequency power be 30~200W.
5. according to the method described in claim 1, it is characterised in that in the step S1, first plasma etching
Etching temperature be 20~100 DEG C.
6. according to the method described in claim 1, it is characterised in that in the step S2, using N2、O2、H2With Ar to first
The V after plasma etchingxOyLayer carries out plasma treatment, preferably described N2, the O2, the H2With the flow of the Ar
Match as 1~3:1~3:1~3:1~3, more preferably described N2Flow be 10~100sccm, the O2Flow for 10~
100sccm, the H2Flow be 5~50sccm, the flow of the Ar is 10~100sccm.
7. according to the method described in claim 1, it is characterised in that in the step S2, the gas of the plasma treatment
Pressure is 3~60mT, and Top electrode radio-frequency power is 100W~800W, and bottom electrode radio-frequency power is 0~100W.
8. according to the method described in claim 1, it is characterised in that the Cl bases gas is selected from Cl2, HCl and BCl3In any
Plant or a variety of.
9. according to the method described in claim 1, it is characterised in that form the VxOyThe material of layer is selected from VO, V2O3、VO2With
V2O5Any of or it is a variety of.
10. according to the method described in claim 1, it is characterised in that before the step S1, methods described also includes following
Step：
Offer is provided with the VxOyThe substrate of layer, in the VxOyThe surface of layer sets mask layer and the mask layer is carved
Erosion, makes the part VxOyLayer is exposed.
11. method according to claim 10, it is characterised in that the mask layer is silicon nitride layer, it is preferred to use carbon fluorine
Base gas carries out the second plasma etching to the mask layer, and is passed through during second plasma etching
O2。
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| CN113948400A (en) * | 2021-10-15 | 2022-01-18 | 无锡尚积半导体科技有限公司 | Process method for improving etching morphology of vanadium oxide |
| CN114171641A (en) * | 2021-11-30 | 2022-03-11 | 北京燕东微电子科技有限公司 | Etching method of vanadium oxide film and manufacturing method of semiconductor device |
| CN114551209A (en) * | 2022-02-24 | 2022-05-27 | 绍兴中芯集成电路制造股份有限公司 | Sensitive device structure, preparation method thereof and semiconductor device |
| CN115148433A (en) * | 2022-06-15 | 2022-10-04 | 无锡尚积半导体科技有限公司 | Method for improving etching morphology of F-based vanadium oxide |
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| CN115148433A (en) * | 2022-06-15 | 2022-10-04 | 无锡尚积半导体科技有限公司 | Method for improving etching morphology of F-based vanadium oxide |
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