CN104843628B - A kind of silicon cantilever structure and preparation method thereof - Google Patents
A kind of silicon cantilever structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of silicon cantilever structure, silicon chip substrate including band cantilever beam, described cantilever beam is etched with groove, it is respectively equipped with multiple borehole structure on two sidewalls of described groove, and the borehole structure on two sidewalls is in being symmetrical arranged one by one, being deposited with sijna rice catalyst layer on each described borehole structure, and every pair is connected by silicon germanium heterojunction nano wire between the most symmetrically arranged borehole structure, described silicon germanium heterojunction nano wire is array structure arrangement.The invention also discloses the preparation method of above-mentioned silicon cantilever structure, silicon cantilever structure of the present invention uses array type silicon germanium heterojunction nano wire as sensitive source, owing to silicon germanium heterojunction nano wire has sensitive piezoresistive characteristic, silicon cantilever structure the most of the present invention has high sensitivity and degree of accuracy；The mask plate of preparation method of the present invention is chromium plate, and chromium plate can make litho pattern resolution higher, so that present configuration is finer.
Description
Technical field
The present invention relates to a kind of with array type silicon germanium heterojunction nano wire for the silicon cantilever structure in sensitive source, further relate to the preparation method of above-mentioned cantilever beam structure, belong to micro-nano mechanical field.
Background technology
Along with the continuous innovation of Technology, minute mechanical and electrical system technology, as the cross discipline of a Bright Prospect, has been realized in basic starting, even has some aspects and achieves application, and the development in future also certainly will be trend of the times.Now, nanotechnology was the most more and more applied to minute mechanical and electrical system along with the requirement to small size development trend, and nanometer technology also achieves significant progress under the requirement improved constantly.And in this big field of nano electromechanical systems, novel nano structure, the little direction such as its preparation process has caused the attention of many researchers.Especially nano wire is in the potential application of sensing direction.Under current technology background, due to the ripe development of silicon technology, people utilize the piezoresistive effect of silicon nanowires to develop some novel pressure sensing structures more.But it is as the innovation of technology, in addition to single silicon nanowires, Ge nanoline, silicon germanium heterojunction nano wire attracts large quantities of researcher to study equally, and it was found that, silicon germanium heterojunction nano wire has sensitiveer piezoresistive characteristic relative to single silicon nanowires or Ge nanoline.These more probabilities just provided for the making of the pressure transducer under nano-scale, the raising for current large scale transducer sensitivity and degree of accuracy is very helpful.
Summary of the invention
The technical problem to be solved is to provide a kind of silicon cantilever structure being sensitive source with array type silicon germanium heterojunction nano wire, silicon cantilever structure of the present invention uses array type silicon germanium heterojunction nano wire as sensitive source, makes silicon cantilever structure of the present invention have higher sensitivity and degree of accuracy.
The present invention also to solve the technical problem that and be to provide the above-mentioned preparation method being sensitive source silicon cantilever structure with array type silicon germanium heterojunction nano wire.
Summary of the invention: for solving above-mentioned technical problem, the technology used in the present invention means are:
A kind of silicon cantilever structure, silicon chip substrate including band cantilever beam, described cantilever beam is etched with groove, it is respectively equipped with multiple borehole structure on two sidewalls of described groove, and the borehole structure on two sidewalls is in being symmetrical arranged one by one, being deposited with sijna rice catalyst layer on each described borehole structure, every pair is connected by silicon germanium heterojunction nano wire between the most symmetrically arranged borehole structure, and described silicon germanium heterojunction nano wire is array structure arrangement.
Wherein, the radius of described silicon germanium heterojunction nano wire is 20 ~ 80 nanometers, and the density of described silicon germanium heterojunction nano-wire array is 30 ~ 80 every square microns.
Wherein, the radius of described sijna rice catalyst layer is 5 ~ 10 nanometers, and the density of described sijna rice catalyst layer is 500 ~ 1200 every square microns.
The preparation method of above-mentioned silicon cantilever structure, comprises the steps:
Step 1, pre-treatment step, monocrystalline silicon sheet surface is carried out thermal oxidation, surface must be arrived and be coated with the monocrystalline silicon piece of silicon dioxide layer；
Step 2, utilizes the chromium plate of required figure to make mask plate, and the lower surface in step 1 monocrystalline silicon piece makes a rectangular window by lithography, with silicon dioxide as mask, is corroded by monocrystalline silicon piece in KOH corrosive liquid, and the degree of depth obtaining window is 225um；
Step 3, utilizes the chromium plate of required figure to make mask plate, in the upper surface gluing of step 2 monocrystalline silicon piece, the upper and lower surface of monocrystalline silicon piece is all directed at lithography mask version, utilizes SUSS litho machine to etch hatch frame at the upper surface of monocrystalline silicon piece；
Step 4, the chromium plate utilizing required figure makees mask plate, upper surface whirl coating set in step 3 monocrystalline silicon piece carves groove structure, utilize photoresist as mask layer, using dry etching silicon process to make the hatch frame degree of depth of step 3 reach 10um, etching silicon is removed photoresist and the conduction oil of monocrystalline silicon piece lower surface after completing and cleans up with deionized water；
Step 5, the monocrystalline silicon piece of step 4 is placed in temperature 78 DEG C, mass percent be 40% KOH solution in corrode, until photoresist mask comes off, groove structure is etched downwards 10um, forms the groove structure needed for cantilever beam；
Step 6, dries the monocrystalline silicon piece front gluing of step 5 and forms protective layer, remove the oxide layer at the cantilever beam back side in buffered hydrofluoric acid solution, and then the photoresist removing front utilizes ICP dry release cantilever beam from the back side；
Step 7, by the oxide layer in photoetching positioning mode elder generation removal step 5 recess sidewall, then carves borehole structure on sidewall；
Step 8, utilizes electrodeposition process to deposit sijna rice catalyst layer on step 7 borehole structure；
Step 9, at a temperature of the monocrystalline silicon piece of step 8 is placed in 450-470 DEG C, first injects phenylsilane liquid in container, and thermal decomposition produces silane gas, using silane gas as precursor gas, utilizes precursor gas to grow silicon nanometer fragment in sijna rice catalyst layer surface；Then cooling the temperature to 420-440 DEG C, stop the growth of silicon nanometer fragment, inject triphenyl germane liquid in container, thermal decomposition produces Germane gas, using Germane gas as precursor gas, grows germanium nanometer fragment in silicon nanometer fragment；So it is concatenated to form the silicon germanium heterojunction nano wire of abrupt interface, until the borehole structure that this silicon germanium heterojunction nano wire is connected in opposing sidewalls.
Wherein, in step 1, the thickness of described silicon dioxide layer is 1.2um.
Wherein, in step 8, concrete operational approach is: be immersed in the microemulsion being made up of mixed solution and surfactant by the monocrystalline silicon piece of step 7, to microemulsion supersound process 20-40 minute, can deposit on borehole structure radius be 5-10 nanometer, density be the sijna rice catalyst layer of the every square micron of 500-1200；Wherein, described mixed solution is 1:6 ~ 15 with the volume ratio of surfactant, described mixed solution is made up of the tin-salt solution that concentration is 0.01-0.05 mol/L and the hydrofluoric acid solution that concentration is 0.2-0.4 mol/L, surfactant is diisooctyl maleate sulfonate and n-heptane solution composition, and the concentration of described surfactant is 0.2-0.4mol/L.
Beneficial effect: use single silicon nanowires or single Ge nanoline as sensitive source compared to silicon cantilever structure in prior art, silicon cantilever structure of the present invention uses silicon germanium heterojunction nano wire as sensitive source, silicon germanium heterojunction nano wire has sensitiveer piezoresistive characteristic than single silicon nanowires or single Ge nanoline, additionally, silicon germanium heterojunction nano wire in silicon cantilever structure of the present invention uses array way arrangement, can effectively solve the problem that and use single nano-wire to cause silicon cantilever structure that sensitivity and the best problem of degree of accuracy occur, silicon cantilever structure of the present invention has high sensitivity and degree of accuracy；Using chromium plate as mask plate in preparation method of the present invention, chromium plate can make the resolution of litho pattern higher, so that silicon cantilever structure of the present invention is more fine, preparation method technique of the present invention is simple, low cost, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural representation of silicon cantilever structure of the present invention；
Fig. 2 is for deposit sijna rice catalyst layer on borehole structure；
Fig. 3 is for grow silicon nanometer fragment in sijna rice catalyst layer surface；
Fig. 4 is growth germanium nanometer fragment in silicon nanometer fragment；
Fig. 5 is growth silicon nanometer fragment in germanium nanometer fragment；
Fig. 6 is the product cross-sectional view that in preparation method of the present invention, step 2 obtains；
Fig. 7 is the product cross-sectional view that in preparation method of the present invention, step 3 obtains；
Fig. 8 is the product cross-sectional view that in preparation method of the present invention, step 4 obtains；
Fig. 9 is the product cross-sectional view that in preparation method of the present invention, step 5 obtains；
Figure 10 is the product cross-sectional view that in preparation method of the present invention, step 6 obtains；
Figure 11 is the product cross-sectional view that in preparation method of the present invention, step 7 obtains；
Figure 12 is the product cross-sectional view that in preparation method of the present invention, step 8 obtains；
Figure 13 is the product cross-sectional view that in preparation method of the present invention, step 9 obtains.
Wherein, silicon chip substrate 1；Borehole structure 2；Groove 3；Silicon germanium heterojunction nano wire 4；Cantilever beam 5；Silicon nanometer fragment 6；Germanium nanometer fragment 7；Sijna rice catalyst layer 8；Silicon dioxide layer 9；Silicon cup window 10；Hatch frame 11；Oxide layer 12；Photoresist layer 13.
Detailed description of the invention
It is further elucidated with the present invention below in conjunction with specific embodiment, it should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention, after having read the present invention, those skilled in the art all fall within the application claims limited range to the amendment of the various equivalent form of values of the present invention.
As shown in Figure 1, the silicon cantilever structure being sensitive source with silicon germanium heterojunction nano wire of the present invention, silicon chip substrate 1 including band cantilever beam 5,4 it is etched with groove 3 on a cantilever beam, it is respectively equipped with multiple borehole structure 2 on 3 two sidewalls of groove, and the borehole structure 2 on two sidewalls is in being symmetrical arranged one by one, sijna rice catalyst layer 8 it is deposited with on each borehole structure 2, every pair is connected by silicon germanium heterojunction nano wire 4 between the most symmetrically arranged borehole structure 2, and silicon germanium heterojunction nano wire 4 is arranged in array structure；The radius of silicon germanium heterojunction nano wire 4 is 20 ~ 80 nanometers, and the density of silicon germanium heterojunction nano wire 4 array is 30 ~ 80 every square microns.
Fig. 2 ~ 5 are the growth flow chart of silicon germanium heterojunction nano wire in silicon cantilever structure of the present invention.
Fig. 6 ~ 13 are the flow chart of silicon cantilever structure preparation method of the present invention, and the preparation method of silicon cantilever structure of the present invention comprises the steps:
Step 1, pre-treatment step: select N-shaped (100) the twin polishing monocrystalline silicon piece 1 of 2 inches, the thickness of monocrystalline silicon piece 1 is 250um, and resistivity is 3 ~ 6 Ω/cm, uses No. 1 and No. 2 cleanout fluid (No. 1 cleanout fluid main component acetone the most respectively；No. 2 cleanout fluid are mainly composed of deionized water) monocrystalline silicon piece 1 is carried out, then the monocrystalline silicon piece 1 after cleaning is carried out thermal oxidation, to arriving surface and be coated with the monocrystalline silicon piece 1 of silicon dioxide layer 9, the thickness of silicon dioxide layer 9 is 1.2um；
Step 2, the chromium plate utilizing required figure makees mask plate, lower surface in step 1 monocrystalline silicon piece 1 makes the silicon cup window 10 that cross section is rectangle by lithography, (taking away chromium plate) is again with silicon dioxide layer 9 as mask, monocrystalline silicon piece 1 is corroded in the KOH corrosive liquid of concentration 40%, the degree of depth obtaining silicon cup window 10 is 225um, and the product figure obtained is as shown in Figure 6；
Step 3; the chromium plate utilizing required figure makees mask plate; upper surface gluing in step 2 monocrystalline silicon piece 1; the upper and lower surface of monocrystalline silicon piece is all directed at lithography mask version; searching out the position of required etching, utilize SUSS litho machine to etch hatch frame 11 at the upper surface of monocrystalline silicon piece 1, this hatch frame 11 position is necessarily above step 2 silicon cup window 10; noting protecting the silicon dioxide layer 9 of monocrystalline silicon piece 1 lower surface, the product figure obtained is as shown in Figure 7；
Step 4, the chromium plate utilizing required figure makees mask plate, upper surface whirl coating set in step 3 monocrystalline silicon piece 1 carves (cantilever beam) groove structure 3, utilize photoresist 13 as mask layer, dry etching silicon process is used to make hatch frame 11 degree of depth of step 3 reach 10um, etching silicon is removed photoresist 13 and the conduction oil of monocrystalline silicon piece 1 lower surface after completing and cleans up with deionized water, and the product figure obtained is as shown in Figure 8；
Step 5, the monocrystalline silicon piece 1 of step 4 is placed in temperature 78 DEG C, mass percent be 40% KOH solution in corrode, until photoresist 13 mask comes off, (now groove structure 3 is etched downwards with hatch frame 11 simultaneously), groove structure 3 is etched downwards 10um, forming the groove structure 3 of cantilever beam 5 desired depth, the product figure obtained is as shown in Figure 9；
Step 6; the monocrystalline silicon piece 1 front gluing of step 5 is dried and forms protective layer; removing the oxide layer at cantilever beam 5 back side in buffered hydrofluoric acid solution, then the photoresist removing front utilizes ICP dry release cantilever beam 5 from the back side, and the product figure obtained is as shown in Figure 10；
Step 7, in single silicon wafer 1 frontal left, silicon area exposed in groove structure 3 forms 30-60um oxide layer 12, oxide layer on removal step 5 groove structure medial wall, photoetching location again, forming the borehole structure 2 for growing silicon germanium heterojunction nano wire 4, the product figure obtained is as shown in figure 11；
Step 8, electrodeposition process is utilized to deposit sijna rice catalyst layer 8 on step 7 borehole structure 2, the monocrystalline silicon piece 1 of step 7 is immersed in the microemulsion being made up of mixed solution and surfactant, to microemulsion supersound process 20-40 minute, can deposit on borehole structure 2 radius be 5-10 nanometer, density be the sijna rice catalyst layer 8 of the every square micron of 500-1200；Wherein, described mixed solution is 1:6 ~ 15 with the volume ratio of surfactant, and described mixed solution is 0.2-0.4 by the tin-salt solution that concentration is 0.01-0.05 mol/L and concentration
The hydrofluoric acid solution composition of mol/L, (tin-salt solution is 1:1 with the volume ratio of hydrofluoric acid solution), surfactant is diisooctyl maleate sulfonate and n-heptane solution composition (diisooctyl maleate sulfonate is 1:1 with the volume ratio of n-heptane solution), the concentration of described surfactant is 0.2-0.4mol/L, and the product figure obtained is as shown in figure 12；
Step 9, efficient solution Meteorological Act (SVG) is used to grow silicon germanium heterojunction nano wire 4, at a temperature of the monocrystalline silicon piece 1 of step 8 is placed in 450-470 DEG C, in container, first inject phenylsilane liquid, thermal decomposition produces silane gas, using silane gas as precursor gas, precursor gas is utilized to go out silicon nanometer fragment 6 in sijna rice catalyst layer 8 superficial growth；Then cooling the temperature to 420-440 DEG C, stop the growth of silicon nanometer fragment 6, inject triphenyl germane liquid in container, thermal decomposition produces Germane gas, using Germane gas as precursor gas, grows germanium nanometer fragment 7 in silicon nanometer fragment 6；So being concatenated to form the silicon germanium heterojunction nano wire of abrupt interface, until the borehole structure 2 that this silicon germanium heterojunction nano wire 4 is connected in opposing sidewalls, finally, utilize buffered hydrofluoric acid solution to remove body structure surface oxide layer 12, the product figure obtained is as shown in figure 13.
The silicon cantilever structure of the present invention, when applying stress at structure (front) right-hand member, cantilever beam 5 can produce strain, and then make the array type silicon germanium heterojunction nano wire sensitivity source 4 in groove 3 produce strain, owing to silicon cantilever structure of the present invention is to use array type silicon germanium heterojunction nano wire as sensitive source, therefore it is far superior to the piezoresistive effect of single silicon nanowires girder construction, and therefore present configuration has the highest sensitivity and degree of accuracy when stress mornitoring.
Claims (6)
1. a silicon cantilever structure, it is characterised in that: use following steps to be prepared from:
Step 1, carries out pretreatment to silicon chip substrate, monocrystalline silicon sheet surface is carried out thermal oxidation, obtains table
Face is coated with the monocrystalline silicon piece of silicon dioxide layer；
Step 2, utilizes the chromium plate of required figure to make mask plate, and the lower surface in step 1 monocrystalline silicon piece makes by lithography
One rectangular window, then with silicon dioxide as mask, monocrystalline silicon piece is corroded in KOH corrosive liquid, obtains
The degree of depth of window is 225um；
Step 3, utilizes the chromium plate of required figure to make mask plate, in the upper surface gluing of step 2 monocrystalline silicon piece,
The upper and lower surface of monocrystalline silicon piece is all directed at lithography mask version, utilizes upper at monocrystalline silicon piece of SUSS litho machine
Surface etches hatch frame；
Step 4, utilizes the chromium plate of required figure to make mask plate, in the upper surface whirl coating set of step 3 monocrystalline silicon piece
Carve groove structure, utilize photoresist as mask layer, use dry etching silicon process to make the hatch frame of step 3
The degree of depth reaches 10um, etching silicon remove after completing photoresist and the conduction oil of monocrystalline silicon piece lower surface and spend from
Sub-water cleans up；
Step 5, the monocrystalline silicon piece of step 4 is placed in temperature 78 DEG C, mass percent be 40% KOH molten
Corroding in liquid, until photoresist mask comes off, groove structure is etched downwards 10um, forms cantilever beam
Required groove structure；
Step 6, dries the monocrystalline silicon piece front gluing of step 5 and forms protective layer, in buffered hydrofluoric acid solution
Removing the oxide layer at the cantilever beam back side, then the photoresist removing front utilizes ICP dry release cantilever from the back side
Beam；
Step 7, by the oxide layer in photoetching positioning mode elder generation removal step 5 recess sidewall, then carves on sidewall
Borehole structure；
Step 8, utilizes electrodeposition process to deposit sijna rice catalyst layer on step 7 borehole structure；
Step 9, at a temperature of the monocrystalline silicon piece of step 8 is placed in 450-470 DEG C, first injects benzene silicon in container
Alkane liquid, thermal decomposition produces silane gas, using silane gas as precursor gas, utilizes precursor gas at sijna
Rice catalyst layer surface grows silicon nanometer fragment；Then cool the temperature to 420-440 DEG C, stop silicon nanometer sheet
The growth of section, injects triphenyl germane liquid in container, and thermal decomposition produces Germane gas, Germane gas is made
For precursor gas, silicon nanometer fragment grows germanium nanometer fragment；The SiGe being so concatenated to form abrupt interface is different
Matter junction nanowire, until the borehole structure that this silicon germanium heterojunction nano wire is connected in opposing sidewalls.
Silicon cantilever structure the most according to claim 1, it is characterised in that: in step 1, described two
The thickness of silicon oxide layer is 1.2um.
Silicon cantilever structure the most according to claim 1, it is characterised in that: in step 8, concrete
Operational approach is: the monocrystalline silicon piece of step 7 is immersed in the microemulsion being made up of mixed solution and surfactant
In, to microemulsion supersound process 20-40 minute, can deposit tin nanoparticles radius on borehole structure is
5～10 nanometers, density is the sijna rice catalyst layer of 500～1200 every square microns；Wherein, described mixing is molten
Liquid is 1: 6～15 with the volume ratio of surfactant, and described mixed solution is 0.01-0.05mol/L's by concentration
Tin-salt solution and the hydrofluoric acid solution composition that concentration is 0.2-0.4mol/L, surfactant is maleic acid two
Different monooctyl ester sulfonate and n-heptane solution composition, the concentration of described surfactant is 0.2-0.4mol/L.
Silicon cantilever structure the most according to claim 1, it is characterised in that: include the silicon of band cantilever beam
Sheet substrate, is etched with groove on described cantilever beam, and two sidewalls of described groove are respectively equipped with multiple circular hole knot
Borehole structure on structure, and two sidewalls, in being symmetrical arranged one by one, each described borehole structure is deposited with sijna
Rice catalyst layer, every pair is connected by silicon germanium heterojunction nano wire between the most symmetrically arranged borehole structure,
Described silicon germanium heterojunction nano wire is array structure arrangement.
Silicon cantilever structure the most according to claim 4, it is characterised in that: described silicon germanium heterojunction is received
The radius of rice noodle is 20～80 nanometers, the density of described silicon germanium heterojunction nano-wire array be 30～80 every square micro-
Rice.
Silicon cantilever structure the most according to claim 4, it is characterised in that: described stannum nanocatalyst
In Ceng, the radius of tin nanoparticles is 5～10 nanometers, and the density of described tin nanoparticles is 500～1200 every square
Micron.
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| CN107271326B (en) * | 2017-07-04 | 2019-10-11 | 西安交通大学 | A kind of MEMS fluid density sensor chip and preparation method thereof based on face interior resonance |
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