CN100457211C - 'I' structured three-dimensional micro solid/hollow silicon needle and silicon knife - Google Patents
'I' structured three-dimensional micro solid/hollow silicon needle and silicon knife Download PDFInfo
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- CN100457211C CN100457211C CNB200610143214XA CN200610143214A CN100457211C CN 100457211 C CN100457211 C CN 100457211C CN B200610143214X A CNB200610143214X A CN B200610143214XA CN 200610143214 A CN200610143214 A CN 200610143214A CN 100457211 C CN100457211 C CN 100457211C
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Abstract
The invention relates to a horizontal three-dimension micro solid/hollow silicon needle or blade used in surgery tools, wherein the needle/blade top prepared by micro-electric technique is horizontal parallel with first group III face of single-crystal silicon; the horizontal top is narrow straight line or curvature on one plane or convex face; one or two sides near the horizontal top or the middle part has triangle, trapezium, hexagon, or similar holes; the holes is through to the bottom of needle/blade via reverse-triangle groove formed by six faces to form through hole. The invention has low cost and high yield, while it can extract micro body liquid, etc.
Description
Technical field
The present invention relates to instrument for microsurgery and Micrometer-Nanometer Processing Technology field, particularly the three-dimensional micro solid of " one " font structure, hollow silicon pin and silicon cutter.
Background technology
The skin of human body has three-layer weave: horny layer, active epidermal area and skin corium.Outermost cuticle thickness is about 10～50 microns, is made up of the horn cell of densification; Be epidermal area below the horny layer, thickness is about 50～100 microns, contains competent cell and very a spot of nervous tissue, but does not have blood vessel.Being skin corium below the epidermal area, is the key component of skin, contains a large amount of living cells, nervous tissue and vascular tissue.Because the external diameter of the injection needle that traditional hypodermic injection uses is generally 0.4～3.4 millimeter, need and go deep into below the skin injection needle transdermal top layer, so that allow the rapid intravasation of medicine, therefore injection process not only is accompanied by pain, and often needs the professional health care personnel to operate.Modern medicine study shows that the skin outermost stratum corneum layer is the major obstacle of drug conveying.Do not go deep into skin corium as long as use micropin or microneedle array that medicine is sent into below the horny layer, medicine will spread rapidly and enter the body circulation by blood capillary.Because the micropin medicine-feeding part does not touch nervous tissue at body surface, therefore can not produce pain; Adopt the micropin administration not need the professional to operate, flexible and convenient to use, interruption of the administration at any time is so accepted by patient easilier.Empty micropin not only can be used for transdermal administration, can also be used for the extraction that transdermal carries out trace body fluid.
At present, report the method for some solid and hollow miniature silicon needle constructions and preparation thereof, comprised following document:
1.S.Henry，D.V.McAllister，M.G.Allen，and?M.R.Prausnitz.Microfabricated?microneedles，“a?novel?approach?to?transdermal?drugdelivery”，J.Pharmaceut.Sci.，87(8)922-925，1998.
2.P.Griss，P.Enoksson，H.K.Tolvanen-Laakso，P.
S.Ollmar，and?G.Stemme，“Micromachined?electrodes?forbiopotential?measurements”，J.Microelectromech.Syst.，10(1)10-16，2001.
3.P.Griss，P.Enoksson，and?G.Stemme，“Micromachinedbarbed?spikes?for?mechanical?chip?attachment”，Sensors?andActuators?A，95：94-99，2002.
4.Patrick?Griss?and
Stemme“Side-Opened?Out-of-PlaneMicroneedles?for?Microfluidic?Transdermal?Liquid?Transfer”，J.Microelectromech.Syst.，12(3)296-301，2003.
5.Han?J.G.E.Gardeniers，Regina?Luttge，Erwin?J.W.Berenschot，Meint?J.de?Boer，Shuki?Y.Yeshurun，Meir?Hefetz，Ronny?van’t?Oever，and?Albert?van?den?Berg，“SiliconMicromachined?Hollow?Microneedles?for?Transdermal?LiquidTransport”，J.Microelectromech.Syst.，12(6)：855-862，2003.
6.E.V.Mukerjee，S.D.Collins，R.R.Isseroff，R.L.Smith，“Microneedle?array?for?transdermal?biological?fluid?extraction?and?insitu?analysis”，Sensors?and?Actuators?A，114：267-275，2004.
7.Boris?Stoeber?and?Dorian?Liepmann，“Arrays?of?HollowOut-of-Plane?Microneedles?for?Drug?Delivery”，J.Microelectromech.Syst.，14(3)472-479，2005.
8.N.Roxhed，P.Griss?and?G.Stemme，“Reliable?In-vivoPenetration?and?Transdermal?Injection?Using?Ultra-sharp?HollowMicroneedles”，Proceedings?of?13th?IEEE?International?Conferenceon?Solid-State?Sensors，Actuators?and?Microsystems，pp.213-216，Seoul，South?Korea，2005.
In above-mentioned document, the needle point of having reported miniature silicon pin generally adopt with the similar conical cylinder structure of traditional sewing needle or with the similar ramp structure of traditional injection needle; The material that uses is the monocrystalline silicon piece in monocrystalline silicon piece or (100) face crystal orientation, manufacture method usually adopts be silicon isotropic etch or with anisotropic etch (comprising wet etching and/or dry etching) process combined, through hole adopts DRIE (deep reactive ion dry etching) equipment to process; For hollow miniature silicon pin, silicon pin inside generally forms and almost vertical circular port of silicon chip surface or slotted eye, and the shape of through hole also is circle or ellipse near the needle point of silicon pin.Because DRIE equipment price costliness, start and maintenance cost height, and belong to monolithic processing, and very consuming time at the thick preparation through hole that reaches on hundreds of microns the monocrystalline silicon piece, so cause the cost of manufacture of hollow miniature silicon pin high, be difficult to realize its practicability.
Summary of the invention
The objective of the invention is to overcome the weakness of existing miniature silicon pin, proposed " one " font structure three-dimensional miniature solid, hollow silicon needle and silicon cutter, its construction features is as follows:
1) pin (cutter) ogival of miniature silicon pin or cutter is " one " font structure parallel with gang (111) face of monocrystal silicon; " one " font structure is the curve on the narrower straight line of width or same plane or the convex surface, and therefore, in some application scenario, this miniature silicon pin comes down to miniature silicon cutter.For example, distinguish according to different purposes, miniature silicon pin is mainly used in puncture, and little cutter can be used for puncture and cutting; For empty micropin or cutter can also be used to puncture or cut after carry out the infusion and the extraction of liquid.In addition, in order to distinguish them, also can define from size, for example, the length of needle point place " " font of miniature silicon pin part is 10 nanometers～50 micron, and width is 0～50 micron; The length of point of a knife place " " the font part of miniature silicon cutter is 50 microns～5 millimeters, and width is 0～300 micron.
2) near one or both sides " one " font structure of the pin of micro hollow silicon needle or cutter (cutter) ogival or in the middle of pin (cutter) ogival " " font structure, have triangle or trapezoidal or hexagon or similar triangle or similar trapezoidal or similar hexagonal hole, and the inverted triangle groove structure that formed by six (111) faces bottom silicon pin or cutter of these holes links to each other and forms through hole;
3) length of miniature solid, hollow silicon needle or point of a knife place " " font part is 10 nanometers～5 millimeter, and width is 0～300 micron;
4) miniature solid, hollow silicon needle or cutter can be the micropin or the cuttves of single or array format;
5) material of miniature silicon pin or cutter employing is a monocrystal silicon; The concrete shape and the size of miniature silicon pin or cutter, the residing position of " one " font structure (centre of pin or cutter or one side) that comprises pin or point of a knife top, the position of through hole, shape (triangle, trapezoidal, hexagon, similar triangle, similar trapezoidal or similar hexagon) and size, the concrete process conditions decision of adopting during by the thickness of the size of the mask pattern on the mask blank, monocrystalline silicon piece and wet etching or dry etching monocrystal silicon.
Described micropin or cutter array can be the arrangements that micropin or cutter carry out according to a determining deviation on same silicon chip, are solid or empty micropin or cutter array, or the mixing array of the two.
The invention allows for a kind of method for preparing micro hollow silicon needle or silicon cutter, may further comprise the steps:
(1) masking film of the anisotropic wet etchant solution that preparation can anti-silicon on the monocrystalline silicon piece in (110) face crystal orientation of cleaning;
(2) optionally remove masking film on the part silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure;
(3) the anisotropic wet etchant solution of putting into silicon carries out anisotropic etch to silicon, forms the del groove structure that is formed by 6 silicon (111) face the most at last;
(4) with the masking film full scale clearance on the silicon chip clean after, at its two sides preparation anisotropy of anti-silicon and the masking film of isotropism wet etching solution simultaneously, the masking film of dry etching that maybe can anti-silicon;
(5) optionally removing silicon chip does not have masking film on the groove one face portion silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, this to parallel edges with that is parallel to that family (111) face on the corresponding silicon chip of parallel edges described in the step (2);
(6) patterned silicon chip in the step (5) is simultaneously carried out corrosion of isotropism and/or anisotropic wet and/or dry etching, finally form hollow silicon needle or silicon cutter;
(7) masking film on the removing silicon chip.
In addition, the invention allows for a kind of method for preparing miniature solid silicon pin or silicon cutter, may further comprise the steps:
(1) masking film of the anisotropic wet etchant solution that preparation can anti-silicon on the monocrystalline silicon piece in (110) face crystal orientation of cleaning;
(2) optionally remove masking film on the part silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure;
(3) patterned silicon chip is simultaneously carried out corrosion of isotropism and/or anisotropic wet and/or dry etching, finally form solid silicon pin or silicon cutter;
(4) masking film on the removing silicon chip.
The invention has the beneficial effects as follows " one " font structure three-dimensional miniature solid, hollow silicon needle or cutter and the array thereof that adopt above-mentioned preparation method to make, do not need the DRIE etching through hole, can realize a plurality of silicon chips are carried out the anisotropic wet corrosion simultaneously, thereby batch machining goes out the del groove that is formed by 6 silicon (111) face on the monocrystalline silicon piece in (110) face crystal orientation, has that technology is simple, reliable, a good reproducibility, fabrication cycle is short, cost is low and yield rate is high advantage.In addition, except that the extraction that can use it for transdermal administration and trace body fluid, also can be used as little cutter and have broad application prospects at biomedical sectors such as microsurgeries.
Description of drawings
Hollow silicon needle that Fig. 1 is tri-angle-holed for both sides have or knife structure sketch map.
The sectional view under single needle diplopore situation of Fig. 2 for being done along the line A-A among Fig. 1.
The sectional view under single needle single hole situation of Fig. 3 for being done along the line A-A among Fig. 1.
Fig. 4 a is the hollow silicon needle of linear structure or the sectional view of cutter for the end face of being done along the line B-B among Fig. 1.
Fig. 4 b is that end face is the hollow silicon needle of curvilinear structures or the sectional view that is similar to Fig. 4 a of cutter.
Fig. 5 is that a side has the hollow silicon needle of trapezoidal hole or the sketch map of knife structure.
The sectional view of Fig. 6 for being done along the line A-A among Fig. 5.
Fig. 7 a is the hollow silicon needle of linear structure or the sectional view of cutter for the end face of being done along the line B-B among Fig. 5.
Fig. 7 b is that end face is the hollow silicon needle of curvilinear structures or the sectional view that is similar to Fig. 7 a of cutter.
Fig. 8 is the structural representation of curve for the cutter end face that has triangle or trapezoidal hole in the middle of needle point " " font structure.
Fig. 9 is tri-angle-holed for the side has, and needle point or cutter end face are the structural representation of convex curved surface.
The sectional view of Figure 10 for being done along the line A-A among Fig. 9.
Figure 11 a is the hollow silicon needle of linear structure or the sectional view of cutter for the end face of being done along the line B-B among Fig. 9.
Figure 11 b is that end face is the hollow silicon needle of curvilinear structures or the sectional view that is similar to Figure 11 a of cutter.
Figure 12 has trapezoidal hole for the side, and needle point or cutter end face are the structural representation of convex curved surface.
The sectional view of Figure 13 for being done along the line A-A among Figure 12.
Figure 14 a is the hollow silicon needle of linear structure or the sectional view of cutter for the end face of being done along the line B-B among Figure 12.
Figure 14 b is that end face is the hollow silicon needle of curvilinear structures or the sectional view that is similar to Figure 14 a of cutter.
The schematic cross-section of Figure 15 inverted triangle groove structure that to be the bottom surface formed by six (111) faces.
The perspective view of Figure 16 for being done along the line A-A among Figure 15.
Figure 17 has pass hollow silicon needle or SEM photo for the both sides of embodiment 1 preparation.
Figure 18 has pass hollow silicon needle or cutter SEM photo for a side of embodiment 1 preparation.
Figure 19 is porose (two holes are obstructed) the type hollow silicon needle in double flute both sides or the cutter array SEM photo of embodiment 1 preparation.
Figure 20 has pass hollow silicon needle or cutter array SEM photo for the single cavity both sides of embodiment 1 preparation.
Figure 21 is the solid silicon pin or the cutter array SEM photo of embodiment 1 preparation.
Figure 22 opens the SEM photo of tri-angle-holed hollow silicon needle or cutter for a side of embodiment 2 preparations.
Figure 23 opens the hollow silicon needle of trapezoidal hole or the SEM photo of cutter for a side of embodiment 2 preparations.
Figure 24 is the hollow silicon needle of embodiment 2 preparations or the SEM photo of cutter array.
Figure 25 is the solid silicon pin of embodiment 2 preparations or the SEM photo of cutter array.
The SEM photo that Figure 26 overlooks for the inverted triangle groove structure that is formed by six (111) faces that adopts potassium hydroxide aqueous solution that the monocrystal silicon in (110) face crystal orientation is carried out that anisotropic etch obtains, groove is at silicon chip surface place formation hexagon.
Figure 27 is preparation technology's flow chart of embodiment 1.
Figure 28 is preparation technology's flow chart of embodiment 2.
Figure 29 is preparation technology's flow chart of embodiment 3.
Figure 30 opens the SEM photo of tri-angle-holed hollow silicon needle or cutter for a side of embodiment 3 preparations.
Figure 31 opens the SEM photo of tri-angle-holed hollow silicon needle or cutter array for another kind one side of embodiment 3 preparations.
Figure 32 is a kind of solid silicon pin of embodiment 3 preparations or the SEM photo of cutter array.
Figure 33 is a kind of distressed structure of Figure 12.
The specific embodiment
The present invention proposes " one " font structure three-dimensional miniature solid, hollow silicon needle or cutter, the structure of described " one " font structure three-dimensional miniature solid, hollow silicon needle or cutter is as follows:
1) the needle point top 1 of miniature silicon pin or cutter is " one " font structure parallel with gang (111) face 5 of monocrystal silicon; " one " font structure is the curve on the narrower straight line of width or same plane or the convex curved surface, therefore the definite miniature silicon cutter (shown in Fig. 1,3,4,9,12) of saying so of this miniature silicon pin.
2) near one or both sides 3 " one " font structure of the needle point end face 1 of micro hollow silicon needle or cutter or in the middle of needle point " " font structure, have triangle or trapezoidal or hexagon or similar triangle or similar trapezoidal or similar hexagonal hole 2 among Fig. 1～Figure 16, and the inverted triangle groove structure 4 that formed by six (111) faces 5 (as Figure 15 with shown in Figure 26) bottom silicon pin or cutter of these holes links to each other and forms through hole;
3) length of miniature solid, hollow silicon needle or point of a knife place " " font part is 10 nanometers～5 millimeter, and width is 0～300 micron.
4) material of miniature silicon pin or cutter employing is a monocrystal silicon; The concrete shape and the size of miniature silicon pin or cutter, the residing position of " one " font structure (centre of pin or cutter or one side) that comprises pin or point of a knife top, the position of through hole, shape (as triangle, trapezoidal, the similar triangle or similar trapezoidal of black in the SEM photo of embodiment) and size, the concrete process conditions decision of adopting during by the thickness of the size of the mask pattern on the mask blank, monocrystalline silicon piece and wet etching or dry etching monocrystal silicon.
Described miniature silicon pin or cutter can be the micropin or the cutter of single or array format; Micropin or cutter array are the arrangements that micropin or cutter carry out according to a determining deviation on same silicon chip, are solid or empty micropin or cutter array, or the mixing array of the two (shown in Figure 20,21,24,25)
Having the micropin of said structure feature or the preparation method of cutter comprises the steps:
1) on the monocrystalline silicon piece of (110) crystal face that polishes, adopt methods such as growth, deposit or coating to prepare masking material layer, masking material can be the thin film of silicon dioxide, silicon nitride, noncrystalline silicon carbide or homogenous materials such as other dielectric material and metal, or the composite membrane of different materials thin film;
2) on the masking material layer that silicon chip one side prepares, apply photoresist, and adopt photoetching, etching figures transfer techniques to obtain patterned masking material layer pattern, this figure has the pair of parallel limit, and this needs parallel with gang's silicon (111) face to parallel edges during photoetching.Utilize the anisotropic etch solution of silicon that silicon chip is carried out the anisotropy etch stop then, thereby obtain relevant with the masking material layer pattern del groove structure that is formed by 6 silicon (111) face, groove forms hexagon (shown in Figure 15,16,26) at the silicon chip surface place;
3) on the masking material layer that the silicon chip opposite side prepares, get rid of photoresist, and adopt double-sided alignment photoetching, etching figures transfer techniques to obtain and the corresponding patterned masking material layer pattern of del groove; This figure has the pair of parallel limit, and this to parallel edges simultaneously and step 2) in that family's silicon (111) face of mentioning parallel.Utilize the isotropism and the anisotropic etch solution of silicon then or adopt isotropism and anisotropic dry etch that silicon chip is carried out isotropic etch and anisotropic etch, form microneedle or the point of a knife and the array thereof of " one " font in this process, the one or both sides face 3 of " one " font structure 1 pin or point of a knife or middle place form having as trapezoidal or similar triangle of triangle or similar trapezoid through hole 2 of linking to each other with del groove 4.
4) material of miniature silicon pin of preparation or cutter employing is the monocrystalline silicon piece in (110) face crystal orientation.5) remove photoresist and masking material layer with dry method or wet processing;
6) the anisotropic etch solution of silicon is meant potassium hydroxide aqueous solution (concentration 10～60wt%), sodium hydrate aqueous solution (concentration 3～50wt%), EPW (ethylenediamine, catechol and water, mol ratio is 20～60%: 0～10%: 40～80%), TMAH (tetramethyl oxyammonia aqueous solution, concentration 5～70wt%).
7) the isotropic etch solution of silicon be meant HNA (Fluohydric acid., nitric acid and acetic acid water solution, volume ratio is respectively 1～30: 2～40: 5～90, in the prescription acid composition be about 49% Fluohydric acid., 70% nitric acid, 99% acetic acid).
8) dry etching of silicon is meant and utilizes dry etching equipment (high pressure plasma etching machine, reactive ion etching machine, inductively coupled plasma etching machine, ion beam milling etc.) to adopt reacting gas or noble gas that silicon is carried out isotropism or anisotropic etching.
9) on monocrystalline silicon piece, the one side that forms silicon pin or point of a knife is carried out in the corrosion process, can hocket to isotropism and the anisotropic wet and/or the dry etching of silicon, implement their order or do not implement one of them, depend on the concrete structure and the size of the silicon pin or the cutter of preparation.
Below in conjunction with embodiment, accompanying drawing and photo the present invention is further described, but is not the microneedle configuration of the present invention's proposition and preparation technology's qualification thereof.
(1) utilizes the microelectronics common process, be on 500 microns the monocrystalline silicon piece 11 in (110) face crystal orientation of cleaning at the thickness of twin polishing, at first adopt thermal oxidation method grow silica membrane 12a, the 12b of 200 nanometers, adopt silicon nitride film 13a, the 13b of LPCVD (low-pressure chemical vapor phase deposition) method deposit 200 nanometers subsequently, shown in Figure 27 (a).
(2) continue to get rid of the photoresist 14a that thickness is about 1 micron in a side of above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13a and silica membrane 12a on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 27 (b).Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure.After in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), removing photoresist 14a and cleaning, the potassium hydroxide aqueous solution of putting into temperature and be 80 ℃, concentration and be 30wt% carries out anisotropic etch to silicon, form the del groove structure that forms by 6 silicon (111) face the most at last, as Figure 27 (c).
(3) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 13a, 13b and silica membrane 12a, 12b and clean up after, utilize the microelectronics common process to adopt thermal oxidation method grow silica membrane 12a ', the 12b ' of 200 nanometers, adopt silicon nitride film 13a ', the 13b ' of LPCVD method deposit 200 nanometers subsequently, shown in Figure 27 (d).
(4) there is not a side of groove to get rid of the photoresist 14b that thickness is about 1 micron at above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13b ' and silica membrane 12b ' on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 27 (e).Figure on the mask blank has the pair of parallel limit, adopts the double-sided alignment litho machine that this is parallel to that family (111) face on the corresponding silicon chip of parallel edges with described in the step (2) that to parallel edges during photolithographic exposure.Among Figure 27 (e) in cross section that A '-A ' locates shown in Figure 27 (f).
(5) after removal photoresist 14b also cleans in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), HNA (volume ratio of Fluohydric acid., nitric acid and acetic acid was respectively 3: 25: the 10) solution of putting into temperature and be 50 ℃ carries out isotropic etch to silicon, in this process, can form microneedle or the point of a knife and the array thereof of in-line, the one or both sides face of " one " font pin or point of a knife or middle place can form link to each other with the del groove have trapezoidal or similar triangle of triangle or a similar trapezoid through hole.Shown in Figure 27 (g).
(6) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 13a ', 13b ' and silica membrane 12a ', 12b ' and clean up, shown in Figure 27 (h), preparation technology's end.The hollow silicon needle of preparation or the SEM photo of cutter comprise:
There are pass hollow silicon needle or cutter SEM photo in the both sides of embodiment 1 preparation shown in Figure 17;
One side of embodiment 1 preparation shown in Figure 18 has pass hollow silicon needle or cutter SEM photo;
Porose (two holes are obstructed) the type hollow silicon needle in double flute both sides or the cutter array SEM photo of embodiment 1 preparation shown in Figure 19;
There are pass hollow silicon needle or cutter array SEM photo in the single cavity both sides of embodiment 1 preparation shown in Figure 20;
The solid silicon pin or the cutter array SEM photo of embodiment 1 preparation shown in Figure 21.
(1) utilizes the microelectronics common process, be on 500 microns the monocrystalline silicon piece 11 in (110) face crystal orientation of cleaning at the thickness of twin polishing, at first adopt thermal oxidation method grow silica membrane 12a, the 12b of 200 nanometers, adopt silicon nitride film 13a, the 13b of LPCVD (low-pressure chemical vapor phase deposition) method deposit 200 nanometers subsequently, shown in Figure 28 (a).
(2) continue to get rid of the photoresist 14a that thickness is about 1 micron in a side of above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13a and silica membrane 12a on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 28 (b).Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure.After in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), removing photoresist 14a and cleaning, the potassium hydroxide aqueous solution of putting into temperature and be 80 ℃, concentration and be 30wt% carries out anisotropic etch to silicon, form the del groove structure that constitutes by 6 silicon (111) face the most at last, shown in Figure 28 (c).
(3) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 13a, 13b and silica membrane 12a, 12b and clean up after, utilize the microelectronics common process to adopt thermal oxidation method grow silica membrane 12a ', the 12b ' of 200 nanometers, adopt silicon nitride film 13a ', the 13b ' of LPCVD (low-pressure chemical vapor phase deposition) method deposit 200 nanometers subsequently, shown in Figure 28 (d).
(4) there is not a side of groove to get rid of the photoresist 14b that thickness is about 1 micron at above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13b ' and silica membrane 12b ' on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 28 (e).Figure on the mask blank has the pair of parallel limit, adopts the double-sided alignment litho machine that this is parallel to that family (111) face on the corresponding silicon chip of parallel edges with described in the step (2) that to parallel edges during photolithographic exposure.Among Figure 28 (e) in cross section that A '-A ' locates shown in Figure 28 (f).
(5) after removal photoresist 14b also cleans in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), HNA (volume ratio of Fluohydric acid., nitric acid and acetic acid is 3: 25: the 10) solution of putting into temperature and be 50 ℃ carries out isotropic etch to silicon, is about 10 microns " one " font microneedle or point of a knife and array thereof shown in Figure 28 (g) can forming the degree of depth in this process.
(6) repeat abovementioned steps (3): after removing silicon nitride film and silica membrane and cleaning up, the silica membrane 12a of 200 nanometers of growing ", 12b " and silicon nitride film 13a ", 13b ".
(7) then, a side that forms microneedle or point of a knife at above-mentioned silicon chip is got rid of the photoresist (not shown) that thickness is about 11 microns, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13b on the part silicon chip then " and silica membrane 12b ", thereby the figure on the mask blank is transferred on the silicon chip.Figure on the mask blank has the pair of parallel limit, and is during photolithographic exposure that this is parallel to that family (111) face on the corresponding silicon chip of parallel edges with described in the step (2) that to parallel edges.
(8) after the removal photoresist also cleans in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), the potassium hydroxide aqueous solution of putting into temperature and be 80 ℃, concentration and be 30wt% carries out anisotropic etch to silicon, corrosion depth is about 100 microns, shown in Figure 28 (h).
(9) then putting into temperature is that 50 ℃ HNA (volume ratio of Fluohydric acid., nitric acid and acetic acid is 3: 25: 10) solution carries out isotropic etch to silicon, the degree of depth that can form " one " font in this process is about 200 microns microneedle or point of a knife and array thereof, the one or both sides face of " one " font pin or point of a knife or middle place can form link to each other with the del groove have trapezoidal or similar triangle of triangle or a similar trapezoid through hole, shown in Figure 28 (i).
(10) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 12a ", 12b " and silica membrane 13a ", 13b " and clean up, shown in Figure 28 (j), preparation technology's end.The hollow silicon needle of preparation or the SEM photo of cutter comprise:
One side of embodiment 2 preparations shown in Figure 22 is opened the SEM photo of tri-angle-holed hollow silicon needle or cutter;
One side of embodiment 2 preparations shown in Figure 23 is opened the hollow silicon needle of trapezoidal hole or the SEM photo of cutter;
The hollow silicon needle of embodiment 2 preparations shown in Figure 24 or the SEM photo of cutter array;
The solid silicon pin of embodiment 2 preparations shown in Figure 25 or the SEM photo of cutter array;
The SEM photo that the inverted triangle groove structure that is formed by six (111) faces that employing potassium hydroxide aqueous solution shown in Figure 26 carries out to the monocrystal silicon in (110) face crystal orientation that anisotropic etch obtains is overlooked, groove is at silicon chip surface place formation hexagon.
(1) utilizes the microelectronics common process, be on 500 microns the monocrystalline silicon piece 11 in (110) face crystal orientation of cleaning at the thickness of twin polishing, at first adopt thermal oxidation method grow silica membrane 12a, the 12b of 200 nanometers, adopt silicon nitride film 13a, the 13b of LPCVD (low-pressure chemical vapor phase deposition) method deposit 200 nanometers subsequently, shown in Figure 29 (a).
(2) continue to get rid of the photoresist 14a that thickness is about 1 micron in a side of above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride film 13a and silica membrane 12a on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 29 (b).Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure.After in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), removing photoresist 14a and cleaning, the potassium hydroxide aqueous solution of putting into temperature and be 80 ℃, concentration and be 30wt% carries out anisotropic etch to silicon, form the del groove structure that constitutes by 6 silicon (111) face the most at last, shown in Figure 29 (c).
(3) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 13a, 13b and silica membrane 12a, 12b and clean up after, utilize the microelectronics common process to adopt thermal oxidation method grow silica membrane 12a ', the 12b ' of 200 nanometers, adopt silicon nitride film 13a ', the 13b ' of LPCVD method deposit 200 nanometers subsequently, shown in Figure 29 (d).
(4) there is not a side of groove to get rid of the photoresist 14b that thickness is about 1 micron at above-mentioned silicon chip, utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove silicon nitride 13b ' and silica membrane 12b ' on the part silicon chip then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 29 (e).Figure on the mask blank has the pair of parallel limit, adopts the double-sided alignment litho machine that this is parallel to that family (111) face on the corresponding silicon chip of parallel edges with described in the step (2) that to parallel edges during photolithographic exposure.Among Figure 29 (e) in cross section that A '-A ' locates shown in Figure 29 (f).
(5) after removal photoresist 14b also cleans in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), continuation is got rid of the photoresist 14b ' that thickness is about 1 micron on the patterned silicon chip surface of step (4), utilize the figure transfer techniques (comprising photoetching and etching) of microelectronics routine optionally to remove part silicon nitride film 13b ' then, thereby the figure on the mask blank is transferred on the silicon chip, shown in Figure 29 (g).
(6) after removal photoresist 14b ' also cleans in the mixed liquor of sulphuric acid that boils and hydrogen peroxide (volume ratio is 3: 1), the potassium hydroxide aqueous solution of putting into temperature and be 80 ℃, concentration and be 30wt% carries out anisotropic etch to silicon, corrosion depth is about 150 microns, shown in Figure 29 (h).
(7) after the use buffered hydrofluoric acid solution is removed silica membrane 12b ' exposed on the silicon chip, shown in Figure 29 (i), put into temperature and be 50 ℃ HNA (Fluohydric acid., the volume ratio of nitric acid and acetic acid is 3: 25: 10) silicon is carried out isotropic etch in the solution, in this process, can form microneedle or point of a knife and the array thereof that the degree of depth is about " one " font of 200 microns, the one or both sides face of " one " font pin or point of a knife or middle place can form link to each other with the del groove have trapezoidal or similar triangle of triangle or a similar trapezoid through hole, shown in Figure 29 (j).
(8) in 40% hydrofluoric acid aqueous solution, remove silicon nitride film 13a ', 13b ' and silica membrane 12a ', 12b ' and clean up, shown in Figure 29 (k), preparation technology's end.The hollow silicon needle of preparation or the SEM photo of cutter comprise:
One side of embodiment 3 preparations shown in Figure 30 is opened the SEM photo of tri-angle-holed hollow silicon needle or cutter;
Another kind one side of embodiment 3 preparations shown in Figure 31 is opened the SEM photo of tri-angle-holed hollow silicon needle or cutter array;
A kind of solid silicon pin of embodiment 3 preparations shown in Figure 32 or the SEM photo of cutter array.
Claims (22)
1. three-dimensional micro silicon pin is characterized in that:
The needle point top of described miniature silicon pin is "-" font structure parallel with gang (111) face of monocrystal silicon; Described "-" font structure is the curve on the narrower straight line of width or same plane or the convex surface; The length of needle point place "-" the font part of miniature silicon pin is 10 nanometers～50 micron, and width is 0～50 micron.
2. miniature silicon pin according to claim 1 is characterized in that: described miniature silicon pin is solid miniature silicon pin.
3. miniature silicon pin according to claim 1 is characterized in that: described miniature silicon pin is hollow miniature silicon pin.
4. miniature silicon pin according to claim 3, it is characterized in that: near side needle point "-" the font structure of described hollow miniature silicon pin or two sides or centre have triangle or trapezoidal or hexagon or similar triangle or similar trapezoidal or similar hexagonal hole, and the inverted triangle groove structure that formed by six (111) faces bottom the silicon pin of these holes links to each other and forms through hole.
5. according to arbitrary described miniature silicon pin in the claim 1 to 3, it is characterized in that: described miniature silicon pin is single or array format.
6. miniature silicon pin according to claim 4 is characterized in that: the material that described miniature silicon pin adopts is a monocrystal silicon; The concrete shape and the size of miniature silicon pin, comprise the centre of silicon pin, the residing position of "-" font structure at needle point top-be or on one side, the position of described through hole, shape and size, the concrete process conditions decision of adopting during by the thickness of the size of the mask pattern on the mask blank, monocrystalline silicon piece and wet etching or dry etching monocrystal silicon.
7. miniature silicon pin according to claim 5, it is characterized in that: described microneedle array is the arrangement that micropin carries out according to a determining deviation on same silicon chip, is solid or empty micropin array, or the mixing array of the two.
8. three-dimensional micro silicon cutter is characterized in that:
The point of a knife top of described miniature silicon cutter is "-" font structure parallel with gang (111) face of monocrystal silicon; Described "-" font structure is the curve on the narrower straight line of width or same plane or the convex surface; The length of point of a knife place "-" the font part of miniature silicon cutter is 50 microns～5 millimeters, and width is 0～300 micron.
9. miniature silicon cutter according to claim 8 is characterized in that: described miniature silicon cutter is solid miniature silicon cutter.
10. miniature silicon cutter according to claim 8 is characterized in that: described miniature silicon cutter is hollow miniature silicon cutter.
11. miniature silicon cutter according to claim 10, it is characterized in that: near side point of a knife "-" the font structure of described hollow miniature silicon cutter or two sides or centre have triangle or trapezoidal or hexagon or similar triangle or similar trapezoidal or similar hexagonal hole, and the inverted triangle groove structure that formed by six (111) faces bottom the silicon cutter of these holes links to each other and forms through hole.
12. arbitrary described miniature silicon cutter in 10 according to Claim 8, it is characterized in that: described miniature silicon cutter is single or array format.
13. miniature silicon cutter according to claim 11 is characterized in that: the material that described miniature silicon cutter adopts is a monocrystal silicon; The concrete shape and the size of miniature silicon cutter, comprise the centre of silicon cutter, the residing position of "-" font structure at point of a knife top-be or on one side, the position of described through hole, shape and size, the concrete process conditions decision of adopting during by the thickness of the size of the mask pattern on the mask blank, monocrystalline silicon piece and wet etching or dry etching monocrystal silicon.
14. miniature silicon cutter according to claim 12 is characterized in that: described little cutter array is the arrangement that little cutter carries out according to a determining deviation on same silicon chip, is solid or hollow little cutter array, or the mixing array of the two.
15. a method for preparing micro hollow silicon needle or silicon cutter may further comprise the steps:
(1) masking film of the anisotropic wet etchant solution that preparation can anti-silicon on the monocrystalline silicon piece in (110) face crystal orientation of cleaning;
(2) optionally remove masking film on the part silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure;
(3) the anisotropic wet etchant solution of putting into silicon carries out anisotropic etch to silicon chip, forms the del groove structure that is formed by 6 silicon (111) face the most at last;
(4) with the masking film full scale clearance on the silicon chip clean after, at its two sides preparation anisotropy of anti-silicon and the masking film of isotropism wet etching solution simultaneously, the masking film of dry etching that maybe can anti-silicon;
(5) optionally removing silicon chip does not have masking film on the groove one face portion silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, and this should be parallel to that family (111) face on the corresponding silicon chip of parallel edges with described in the step (2) that to parallel edges during photoetching;
(6) patterned silicon chip in the step (5) is simultaneously carried out corrosion of isotropism and/or anisotropic wet and/or dry etching, final hollow silicon needle or the silicon cutter of forming, the needle point top of described miniature silicon pin or the point of a knife top of described miniature silicon cutter are "-" font structure parallel with gang (111) face of monocrystal silicon; Described "-" font structure is the curve on the narrower straight line of width or same plane or the convex surface; The length of point of a knife place "-" the font part of the needle point place of miniature silicon pin or miniature silicon cutter is 10 nanometers～50 micron, and width is 0～50 micron;
(7) masking film on the removing silicon chip.
16. method according to claim 15 is characterized in that, also comprises the following step that is positioned between step (5) and the step (6):
In to step (5), optionally remove the masking film on the part silicon chip on the patterned silicon chip one side, thereby the figure on another piece mask blank is transferred on the silicon chip.
17. method according to claim 15 is characterized in that:
The masking film of preparation is silicon dioxide or silicon nitride or the composite membrane of the two in step (1) and/or step (4).
18. method according to claim 15 is characterized in that:
The anisotropic wet etchant solution of silicon is potassium hydroxide aqueous solution, sodium hydrate aqueous solution, EPW or TMAH; The isotropism wet etching liquid of silicon is HNA.
19. a method for preparing miniature solid silicon pin or silicon cutter may further comprise the steps:
(1) masking film of the anisotropic wet etchant solution that preparation can anti-silicon on the monocrystalline silicon piece in (110) face crystal orientation of cleaning;
(2) optionally remove masking film on the part silicon chip, thereby the figure on the mask blank is transferred on the silicon chip; Figure on the mask blank has the pair of parallel limit, and this should be parallel with gang (111) face on the silicon chip to parallel edges during photolithographic exposure;
(3) patterned silicon chip is simultaneously carried out corrosion of isotropism and/or anisotropic wet and/or dry etching, final solid silicon pin or the silicon cutter of forming, the needle point top of described miniature silicon pin or the point of a knife top of described miniature silicon cutter are "-" font structure parallel with gang (111) face of monocrystal silicon; Described "-" font structure is the curve on the narrower straight line of width or same plane or the convex surface; The length of point of a knife place "-" the font part of the needle point place of miniature silicon pin or miniature silicon cutter is 10 nanometers～50 micron, and width is 0～50 micron;
(4) masking film on the removing silicon chip.
20. method according to claim 19 is characterized in that, also comprises being positioned between step (2) and the step (3) or the intermediary following step of step (3):
Optionally remove the masking film on the part silicon chip on to patterned silicon chip one side, thereby the figure on another piece mask blank is transferred on the silicon chip.
21. method according to claim 19 is characterized in that:
The masking film of preparation is silicon dioxide or silicon nitride or the composite membrane of the two in step (1) and/or step (4).
22. method according to claim 19 is characterized in that:
The anisotropic wet etchant solution is potassium hydroxide aqueous solution, sodium hydrate aqueous solution, EPW or TMAH; The isotropism wet etching liquid of silicon is HNA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610143214XA CN100457211C (en) | 2006-04-10 | 2006-10-31 | 'I' structured three-dimensional micro solid/hollow silicon needle and silicon knife |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610072807.1 | 2006-04-10 | ||
| CNA2006100728071A CN1830496A (en) | 2006-04-10 | 2006-04-10 | '-'-shaped structure three-dimensional micre solid, hollow silicone meedle orknife |
| CNB200610143214XA CN100457211C (en) | 2006-04-10 | 2006-10-31 | 'I' structured three-dimensional micro solid/hollow silicon needle and silicon knife |
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| CN100457211C true CN100457211C (en) | 2009-02-04 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002239014A (en) * | 2001-02-19 | 2002-08-27 | Sumitomo Precision Prod Co Ltd | Needle-like body and method for manufacturing needle- like body |
| US6503231B1 (en) * | 1998-06-10 | 2003-01-07 | Georgia Tech Research Corporation | Microneedle device for transport of molecules across tissue |
| CN1526454A (en) * | 2003-03-06 | 2004-09-08 | 财团法人工业技术研究所 | Manufacture of micro syringe array |
| CN1569271A (en) * | 2003-12-26 | 2005-01-26 | 中国科学院理化技术研究所 | Minisize solid silicon needle array chip and its preparation method and use |
| US20050261632A1 (en) * | 2004-05-18 | 2005-11-24 | Bai Xu | High-Aspect-Ratio Microdevices and Methods for Transdermal Delivery and Sampling of Active Substances |
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- 2006-10-31 CN CNB200610143214XA patent/CN100457211C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503231B1 (en) * | 1998-06-10 | 2003-01-07 | Georgia Tech Research Corporation | Microneedle device for transport of molecules across tissue |
| JP2002239014A (en) * | 2001-02-19 | 2002-08-27 | Sumitomo Precision Prod Co Ltd | Needle-like body and method for manufacturing needle- like body |
| CN1526454A (en) * | 2003-03-06 | 2004-09-08 | 财团法人工业技术研究所 | Manufacture of micro syringe array |
| CN1569271A (en) * | 2003-12-26 | 2005-01-26 | 中国科学院理化技术研究所 | Minisize solid silicon needle array chip and its preparation method and use |
| US20050261632A1 (en) * | 2004-05-18 | 2005-11-24 | Bai Xu | High-Aspect-Ratio Microdevices and Methods for Transdermal Delivery and Sampling of Active Substances |
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