CN104992905B - A kind of boron nitride substrate surface step lithographic method - Google Patents
A kind of boron nitride substrate surface step lithographic method Download PDFInfo
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- CN104992905B CN104992905B CN201510307155.4A CN201510307155A CN104992905B CN 104992905 B CN104992905 B CN 104992905B CN 201510307155 A CN201510307155 A CN 201510307155A CN 104992905 B CN104992905 B CN 104992905B
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 96
- 239000000758 substrate Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- 239000010410 layer Substances 0.000 claims abstract description 58
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 9
- 239000002356 single layer Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims description 13
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000001039 wet etching Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000010894 electron beam technology Methods 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 238000004549 pulsed laser deposition Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000869 ion-assisted deposition Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001672694 Citrus reticulata Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30612—Etching of AIIIBV compounds
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Drying Of Semiconductors (AREA)
Abstract
The present invention provides a kind of boron nitride substrate surface step lithographic method, comprises the following steps:S1:One hexagonal boron nitride substrate is provided;S2:Mask layer is formed in the hexagonal boron nitride substrate surface, and the default etched features for exposing the hexagonal boron nitride substrate surface are formed in the mask layer;S3:The deposited metal layer in the mask layer surface and the default etched features;S4:Peel off the mask layer and its metal level on surface;S5:The hexagonal boron nitride substrate is annealed, then removes the metal level in the default etched features, the step of single-layer silicon nitride boron atom thickness is obtained in the hexagonal boron nitride substrate surface.The present invention can not only control the patterned shape of hexagonal boron nitride, size, it is also an option that etch areas, while the height of control etching step, can solve the graphical processing problem based on hexagonal boron nitride thin-film device by etching repeatedly.
Description
Technical field
The invention belongs to technical field of semiconductors, is related to a kind of boron nitride substrate surface step lithographic method.
Background technology
The new low-dimension nano material such as discovery of graphene, boron nitride, CNT etc. in recent years and successfully prepare, turn into
The focus of condensed state area research, as their unique novel physicochemical properties are gradually found by people, in micro-nano electricity
Sub- devices field shows huge application prospect.
Hexagonal boron nitride (h-BN) is a kind of similar with graphene-structured with SP2The stratiform hexagonal lattice nanometer material of bonding
Material, is commonly called as white graphite alkene.Hexagonal boron nitride has similar physical property with graphene, such as good thermal conductivity and stability,
High temperature resistant and corrosivity, high rigidity and chemical stability etc..Due to its have the surface of atomically flating, without dangling bonds, without electricity
Son doping, and it is considered as a kind of preferable substrate of graphene electronics device.Simultaneously because the ion bonding of hexagonal boron nitride
Mode is different with graphene, therefore also shows for example wide band gap of the different physical property of graphene, high resistivity, low Jie
Electric constant etc..These excellent characteristics cause boron nitride nanosheet to have good application prospect in many aspects, such as using
The semiconductor microelectronics device that is worked under high temperature, feds, high temperature heat transfer composite, photoelectric material etc..
But relative to graphene, the preparation method of boron nitride nanosheet is not a lot.This is primarily due to six sides nitridation
There is the feature of ionic bond, this can cause the model moral of the force ratio graphite layers of its interlayer between two neighboring lamella in boron
Magnificent power is eager to excel, it is difficult to which image-stone ink is like that peeled away hexagonal boron nitride by conventional method.
In order to meet the needs of h-BN devices preparation, the graphical processing technology of h-BN films is particularly important.Currently
The h-BN graphically more methods using photoetching binding plasma etching of etching, or used in chemical gas-phase deposition system
Gas carries out reactive ion etching, and these methods can not control the number of plies or thickness of etching well.
Therefore, a kind of boron nitride substrate surface step lithographic method how is provided, so that the step etching number of plies or thickness can
Control, turns into those skilled in the art's important technological problems urgently to be resolved hurrily.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of boron nitride substrate surface step
Lithographic method, it is applied to the knot that micro-nano electronics, photoelectric device and integrated circuit etc. run into for solving h-BN in the prior art
The graphical problem of structure.
In order to achieve the above objects and other related objects, the present invention provides a kind of boron nitride substrate surface step etching side
Method, comprise the following steps:
S1:One hexagonal boron nitride substrate is provided;
S2:Form mask layer in the hexagonal boron nitride substrate surface, and formed in the mask layer expose it is described
The default etched features of hexagonal boron nitride substrate surface;
S3:The deposited metal layer in the mask layer surface and the default etched features;
S4:Peel off the mask layer and its metal level on surface;
S5:The hexagonal boron nitride substrate is annealed, then removes the metal level in the default etched features,
The hexagonal boron nitride substrate surface obtains the step of single-layer silicon nitride boron atom thickness.
Alternatively, the mask layer includes photoresist or hard mask plate.
Alternatively, during the default etched features are formed in the mask layer, using uv-exposure method, electronics
Beam exposure method, X-ray exposure method, ion beam exposure method or nano-imprint method form the default etching figure in the mask layer
The litho pattern of shape.
Alternatively, the metal level is elemental metals Ni, Al, Zn, Mg, Fe, Sn, Pb or Co, or the metal level is institute
State the alloy of elemental metals.
Alternatively, the thickness of the metal level is 2~100nm.
Alternatively, the method for depositing the metal level is electron-beam vapor deposition method, sputtering method, ion assisted deposition method or pulse
Laser deposition.
Alternatively, the atmosphere of the annealing is Ar/H2Mixed gas, gas flow ratio 200:100~200:20, annealing
Temperature range is 200~1000 DEG C, and annealing time is 2~8 hours.
Alternatively, the metal level in the default etched features is removed using wet etching.
Alternatively, the wet etching is using HCl, (NH4)2S2O8、HNO3、H2SO4Or acetic acid solution.
Alternatively, the concentration of the solution is 0.01~0.2mol/L, and wet etching soak time is 1min~10hour.
Alternatively, the hexagonal boron nitride substrate is obtained using mechanical stripping or chemical vapour deposition technique.
Alternatively, after the step S5, repeating said steps S2~S5 at least once, in the boron nitride substrate table
Face obtains the step of preset thickness.
As described above, the boron nitride substrate surface step lithographic method of the present invention, has the advantages that:The present invention's
Boron nitride substrate surface step lithographic method, by forming default etched features in the mask layer on hexagonal boron nitride surface, with
Deposited metal afterwards so that the hexagonal boron nitride underlayer surface in default etched features region produces defect, then peels off default etching
Mask layer around figure and metal thereon, and the hexagonal boron nitride substrate is annealed, to promote metal and be broken
The dangling bonds combination bonding on bad hexagonal boron nitride surface, then the metal in default etched features, metal quilt are removed using solution
The destroyed hexagonal boron nitride atom in pre-etching region top layer is taken away during dissolving, forms the step of individual layer atomic thickness.This method
It can not only control the patterned shape of hexagonal boron nitride, size, it is also an option that etch areas, while by etching repeatedly,
The height of etching step can be controlled, solves the graphical processing problem based on hexagonal boron nitride thin-film device.
Brief description of the drawings
Fig. 1 is shown as the process chart of the boron nitride substrate surface step lithographic method of the present invention.
Fig. 2 is shown as the structural representation of hexagonal boron nitride substrate in the boron nitride substrate surface step lithographic method of the present invention
Figure.
Fig. 3 is shown as in the boron nitride substrate surface step lithographic method of the present invention in the hexagonal boron nitride substrate surface
Mask layer is formed, and showing for the default etched features for exposing the hexagonal boron nitride substrate surface is formed in the mask layer
It is intended to.
Fig. 4 is shown as in the boron nitride substrate surface step lithographic method of the present invention in the mask layer surface and described pre-
If the schematic diagram of deposited metal layer in etched features.
Fig. 5 is shown as peeling off the mask layer and its surface in the boron nitride substrate surface step lithographic method of the present invention
The schematic diagram of metal level.
Fig. 6 is shown as removing in the default etched features in the boron nitride substrate surface step lithographic method of the present invention
Metal level, the schematic diagram of the step of single-layer silicon nitride boron atom thickness is obtained in the hexagonal boron nitride substrate surface.
Fig. 7 is shown as in the boron nitride substrate surface step lithographic method of the present invention weight on the basis of structure shown in Fig. 6
At least once, the step that nitride multilayer boron atom thickness is obtained in the boron nitride substrate surface shows by the multiple step S2~S5
It is intended to.
Component label instructions
S1~S5 steps
1 hexagonal boron nitride substrate
2 mask layers
3 default etched features
4 metal levels
5 steps
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Fig. 1 is referred to Fig. 7.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, the component relevant with the present invention is only shown in schema then rather than according to package count during actual implement
Mesh, shape and size are drawn, and kenel, quantity and the ratio of each component can be a kind of random change during its actual implementation, and its
Assembly layout kenel may also be increasingly complex.
The present invention provides a kind of boron nitride substrate surface step lithographic method, referring to Fig. 1, being shown as the technique of this method
Flow chart, comprise the following steps:
S1:One hexagonal boron nitride substrate is provided;
S2:Form mask layer in the hexagonal boron nitride substrate surface, and formed in the mask layer expose it is described
The default etched features of hexagonal boron nitride substrate surface;
S3:The deposited metal layer in the mask layer surface and the default etched features;
S4:Peel off the mask layer and its metal level on surface;
S5:The hexagonal boron nitride substrate is annealed, then removes the metal level in the default etched features,
The hexagonal boron nitride substrate surface obtains the step of single-layer silicon nitride boron atom thickness.
Technical scheme is described in detail below by specific example.
Embodiment one
Referring initially to Fig. 2, step S1 is performed:One hexagonal boron nitride substrate 1 is provided.
Specifically, the hexagonal boron nitride substrate 1 can use mechanical stripping or chemical vapour deposition technique to obtain.
Mechanical stripping method is usually:Hexagonal boron nitride block is pasted onto on adhesive tape, multiple doubling adhesive tape, peels off nitrogen layer by layer
Change boron block, until leaving relatively thin hexagonal boron nitride film on adhesive tape, and be transferred to target substrate such as SiO2, quartz or
In flexible substrate.
Chemical vapour deposition technique is usually:Using metal catalytic substrate, such as Cu, Ni or Pt, with BH3NH3、(HBNH)3、
(HBNCl)3Or (ClNH)3Deng for growth source, under preset process condition, grow to obtain hexagonal nitrogen in metal catalytic substrate surface
Change boron membrane.This is well known to those skilled in the art, and here is omitted.
Referring next to Fig. 3, step S2 is performed:Mask layer 2 is formed on the surface of hexagonal boron nitride substrate 1, and in institute
State the default etched features 3 for being formed in mask layer 2 and exposing the surface of hexagonal boron nitride substrate 1.
Specifically, according to the type of device to be made and can require flexibly to control the position of the default etched features,
That is selective etching region.The form and dimension of the default etched features can be equally configured by changing litho pattern.
Specifically, the mask layer 2 can be photoresist or hard mask version.In the present embodiment, the mask layer 2 is preferably
Photoresist, it can be formed by photoetching processes such as linging, spin coating photoresists.Subsequently through photoetching processes such as alignment exposures described
The litho pattern of default etched features is formed in mask layer 2, then it is developed, obtain the default etched features 3.The exposure can
The methods of using uv-exposure method, electron beam exposure method, X-ray exposure method, ion beam exposure method or nano impression.
Then referring to Fig. 4, performing step S3:The deposition gold in the surface of mask layer 2 and the default etched features 3
Belong to layer 4.
Specifically, the metal level 4 is elemental metals Ni, Al, Zn, Mg, Fe, Sn, Pb or Co, or the metal level 4 is
The alloy of the elemental metals.The thickness of the metal level 4 is 2~100nm.The method for depositing the metal level 4 is electron beam
Evaporation, sputtering method, ion assisted deposition method or pulsed laser deposition.
Electron-beam vapor deposition method is one kind of vacuum vapor plating, is to be directly heated under vacuum using electron beam
Material is evaporated, evaporation material is gasified and is transported to substrate, the method for forming film is condensed in substrate.Heat and fill in electron beam
In putting, heated material is positioned in the mandarin orange whirlpool of water cooling, can avoid evaporating material and reacting with mandarin orange misfortune wall influenceing film
Quality, therefore, electron beam vapor deposition method can prepare high purity films.Electron beam evaporation can evaporate materials with high melting point, than one
As the resistance heating evaporation thermal efficiency is high, beam current density is big, evaporation rate is fast, manufactured film purity is high, quality is good, and thickness can be with
Accurately control.
Sputtering (sputtering) is one kind of PVD film preparing technologies, is broadly divided into four major classes:D.c. sputtering, exchange
Sputtering, reactive sputtering and magnetron sputtering.Sputtered film is typically to be produced in the plasma of inert gas (such as argon).Sputtering
Principle is to use charged particle bombardment target, during the Ions Bombardment surface of solids of acceleration, surface atom occurs and collides and energy occurs
With the transfer of momentum, target atom is escaped from surface and be deposited on the process on backing material.Due to sputter procedure contain it is dynamic
The conversion of amount, so the particle sputtered is directive.Using sputtering can make substrate material surface obtain metal, alloy or
Thin dielectric film.Have that substrate temperature is low using sputtering technology, film matter is pure, and even tissue is closely knit, fastness and favorable reproducibility
The advantages that.
Ion assisted deposition (ion assisted deposition) is while electron beam evaporation or deposition, with one
The surface that surely amount, species, the strong ion beam bombardment of stream are growing is to improve a kind of method of film quality.
Pulsed laser deposition (Pulsed Laser Deposition, PLD), also referred to as pulse laser ablation (pulsed
Laser ablation, PLA), it is that one kind is bombarded object using laser, then will pounds the species precipitate come not
With substrate on, precipitated or a kind of means of film.PLD can be generally divided into the following four stage:Laser emission with
The interaction stage of target, the movement segment of melted material, melted material are in the depositional phase of substrate and film in substrate surface
Nucleation (nucleation) and generation phase.Pulsed laser deposition has good guarantor's composition, sedimentation rate height, experiment
Cycle is short, underlayer temperature requires that film that is low, preparing is uniform, technological parameter is arbitrarily adjusted, the species of target is not limited
Advantage.
As an example, use W metal of the sputtering method in body structure surface deposit thickness shown in Fig. 3 for 10nm.
Particularly, during deposited metal, due to the impact of energetic atom or ion, in the default etched features 3
The surface of hexagonal boron nitride substrate 1 can produce defect, so as to destroy hexagonal boron nitride surface structure.
Again referring to Fig. 5, performing step S4:Peel off the mask layer 2 and its metal level 4 on surface.
Because the mask layer 2 uses photoresist, it is easy to be stripped, metal level 4 thereon also can be in photoresist lift off
During be pulled away, only leave the metal level in default etched features region.
Finally referring to Fig. 6, performing step S5:The hexagonal boron nitride substrate is annealed, then removed described pre-
If the metal level 4 in etched features 3, the step of single-layer silicon nitride boron atom thickness is obtained on the surface of hexagonal boron nitride substrate 1
5。
Particularly, the purpose of annealing is to promote the dangling bonds combination bonding of metal and destroyed hexagonal boron nitride surface,
In favor of the hexagonal boron nitride atom of skim-coat can be removed during follow-up removal metal well simultaneously, realize to hexagonal boron nitride substrate
Corrasion.
Specifically, the atmosphere of the annealing is Ar/H2Mixed gas, gas flow ratio 200:100~200:20, annealing
Temperature range is 200~1000 DEG C, and annealing time is 2~8 hours.It is low using 600 DEG C preferably in CVD stoves in the present embodiment
Pressure annealing 2~6 hours.
Specifically, the metal level 4 in the default etched features 3 is removed using wet etching.The wet etching uses
HCl、(NH4)2S2O8、HNO3、H2SO4Or acetic acid solution.The concentration of the solution is 0.01~0.2mol/L, and wet etching soaks
Time is 1min~10hour.
As an example, structure shown in Fig. 5 by annealing is put into the NH4 that concentration is 0.02%)2S2O8In solution, normal temperature
Immersion 1 hour, is completely dissolved the metal on h-BN surfaces.
Because metal is in deposition process, a certain degree of destruction can be formed to surface h-BN atomic layers, so that
Hexagonal boron nitride surface forms dangling bonds, and annealing process makes this layer of destroyed hexagonal boron nitride form chemical bond with metal, or
Person is dissolved in a metal.Therefore during wet etching dissolves metal level, one layer of hexagonal boron nitride original below metal level
Sublayer will be pulled away so as to obtain the step 5 of single-layer silicon nitride boron atom thickness.
Particularly, due to the lower section of the metal level 4 of graphics field destroyed top layer hexagonal boron nitride atom and metal
Between there is adhesion, therefore during metal level is dissolved, one layer of h-BN atomic layer below metal level will be pulled away
(be similar to when rainwater washes away sand and also taken away the mud glued on sand), so as to obtain the institute of single-layer silicon nitride boron atom thickness
State step 5.
So far, etch to have obtained the step of single-layer silicon nitride boron atom thickness in the hexagonal boron nitride substrate surface.
Embodiment two
Referring to Fig. 7, the present embodiment on the basis of embodiment one repeating said steps S2~S5 at least once, described
Boron nitride substrate surface obtains the step of preset thickness.
Specifically, during repeating said steps S2, same photomask can be used, formed above original step
Mask lithography figure, technique is simple, and will not increase mask costs.
In summary, boron nitride substrate surface step lithographic method of the invention, passes through covering on hexagonal boron nitride surface
Default etched features, subsequent deposited metal are formed in film layer so that the hexagonal boron nitride underlayer surface in default etched features region
Defect is produced, then peels off the mask layer around default etched features and metal thereon, and to the hexagonal boron nitride substrate
Annealed, to promote the dangling bonds combination bonding of metal and destroyed hexagonal boron nitride surface, then it is pre- using solution removal
If the metal in etched features, metal takes away the destroyed hexagonal boron nitride atom in pre-etching region top layer when being dissolved, formed
The step of individual layer atomic thickness.This method can not only control the patterned shape of hexagonal boron nitride, size, it is also an option that carving
Region is lost, while by etching repeatedly, the height of etching step can be controlled, solved based on hexagonal boron nitride thin-film device
Graphical processing problem.So the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (12)
1. a kind of boron nitride substrate surface step lithographic method, it is characterised in that comprise the following steps:
S1:One hexagonal boron nitride substrate is provided;
S2:Mask layer is formed in the hexagonal boron nitride substrate surface, and is formed in the mask layer and exposes the hexagonal
The default etched features of boron nitride substrate surface;
S3:The deposited metal layer in the mask layer surface and the default etched features;
S4:Peel off the mask layer and its metal level on surface;
S5:The hexagonal boron nitride substrate is annealed, the metal level in the default etched features is then removed, described
Hexagonal boron nitride substrate surface obtains the step of single-layer silicon nitride boron atom thickness.
2. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:The mask layer includes
Photoresist or hard mask version.
3. boron nitride substrate surface step lithographic method according to claim 2, it is characterised in that:In the mask layer
During forming the default etched features, exposed using uv-exposure method, electron beam exposure method, X-ray exposure method, ion beam
Light method or nano-imprint method form the litho pattern of the default etched features in the mask layer.
4. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:The metal level is single
Matter W metal, Al, Zn, Mg, Fe, Sn, Pb or Co, or the alloy that the metal level is the elemental metals.
5. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:The thickness of the metal level
Spend for 2~100nm.
6. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:Deposit the metal level
Method be electron-beam vapor deposition method, sputtering method, ion assisted deposition method or pulsed laser deposition.
7. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:The atmosphere of the annealing
For Ar/H2Mixed gas, gas flow ratio 200:100~200:20, annealing region is 200~1000 DEG C, during annealing
Between be 2~8 hours.
8. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:Gone using wet etching
Except the metal level in the default etched features.
9. boron nitride substrate surface step lithographic method according to claim 8, it is characterised in that:The wet etching is adopted
With HCl, (NH4)2S2O8、HNO3、H2SO4Or acetic acid solution.
10. boron nitride substrate surface step lithographic method according to claim 9, it is characterised in that:The solution it is dense
It is 1min~10hour to spend for 0.01~0.2mol/L, wet etching soak time.
11. boron nitride substrate surface step lithographic method according to claim 1, it is characterised in that:The hexagonal nitridation
Boron substrate is obtained using mechanical stripping or chemical vapour deposition technique.
12. the boron nitride substrate surface step lithographic method according to claim 1~11 any one, it is characterised in that:
After the step S5, repeating said steps S2~S5 obtains preset thickness at least once, in the boron nitride substrate surface
Step.
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