CN105217565A - A kind of preparation method of monocrystalline silicon empty micropin structure - Google Patents
A kind of preparation method of monocrystalline silicon empty micropin structure Download PDFInfo
- Publication number
- CN105217565A CN105217565A CN201410253151.8A CN201410253151A CN105217565A CN 105217565 A CN105217565 A CN 105217565A CN 201410253151 A CN201410253151 A CN 201410253151A CN 105217565 A CN105217565 A CN 105217565A
- Authority
- CN
- China
- Prior art keywords
- silicon chip
- silicon
- micropin
- photoresist
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00111—Tips, pillars, i.e. raised structures
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
- A61M2037/0053—Methods for producing microneedles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2201/00—Specific applications of microelectromechanical systems
- B81B2201/05—Microfluidics
- B81B2201/055—Microneedles
Abstract
The invention discloses the preparation method of the different plane hollow microneedle structure of a kind of monocrystalline silicon, in an exemplary embodiments, the method can comprise: first make non-penetrating poroid groove at the dark silicon dry etching method of (100) type front side of silicon wafer; Thick oxide layer is formed at silicon chip positive and negative and hole inwall by thermal oxidation process; Corrosion window graphics is formed respectively at front side of silicon wafer and back side gluing photoetching method; With dry method or wet etching method, the silica in window is removed, expose substrate silicon; With Silicon Crystal Anisotropic Etching liquid, silicon chip is corroded after removing photoresist, microneedle configuration is formed at upper surface, lower surface forms bathtub construction, and the deep hole that previously etching had been formed runs through front side of silicon wafer microneedle configuration, and bottom is connected with the bathtub construction of silicon chip back side.Present invention process is simple, and with low cost, yield rate is high, be applicable in enormous quantities manufacture, and the micropin that obtains has the advantages such as structural strength is large, uniformity good, and medicine carrying dosage is large, has application prospect at biomedical sector.
Description
Technical field
The present invention relates to the preparation method of the different plane hollow microneedle structure of a kind of monocrystalline silicon, belong to MEMS micro-nano technology field.
Background technology
Convenient administration mode is oral administration and intravenous administration, and they are administering modes very easily, can meet the demand of most of medicine.But these two kinds of administering modes also have respective shortcoming.Oral administration is due to will through alimentary canals such as stomach and intestine, and through metabolism, the drug effect of a lot of medicine especially protein drug reduces.Intravenous administration not only needs professional to operate, and can cause pain to patient, is not suitable for long-term successive administration.In order to overcome above-mentioned limitation, the micropin utilizing MEMS technology to make is for administration field, open up a kind of new administering mode-microneedle cutaneous, not only can be used for macro-molecular protein class drug administration, and meet the demand of painless, Wicresoft, successive administration.
Micropin thrusts skin, defines real physical channel, and applicable macromolecular drug passes through.According to ideal situation, as long as micropin pierces through cuticula, medicine just can infiltrate in skin and enter blood circulation system, so the desirable design length of micropin only needs tens microns, but the micropin length of research in fact now, all hundreds of micron even several millimeters, arrived epidermal area even skin corium, but bibliographical information is still painless, it is low that reason may be that the micropin of small size like this encounters neural probability, and the pain that the pain that micropin is produced produces than intravenous injection gentlier [document 1].Although micropin causes real physical channel at skin, because micropin size is smaller at micron order, the infringement caused skin is very little.If micropin and Micropump and micro-fluidic chip etc. form intelligent drug delivery system, so just can the medication amount of Real-Time Monitoring client need, realize real-time continuous administration.Therefore, compare other administering modes, micropin can realize painless, Wicresoft and successive administration.
From manufacture craft point, micropin can be divided into isoplanar micropin and different plane micropin [document 2,3] two kinds.The axis parallel of isoplanar micropin is in substrate surface, and the axis perpendicular of different plane micropin is in substrate surface.The shortcoming of isoplanar micropin is difficult to make three-dimensional microneedle array, and micropin number is less.The pluses and minuses of different plane micropin are on the contrary, and advantage is that micropin number is more, can make three-dimensional microneedle array; Shortcoming is that the height of micropin is restricted, and the technics comparing making different plane micropin is complicated.
From internal structure point, micropin can be divided into empty micropin and solid microneedles according to inside with or without fluid channel.Their administering mode is different: solid microneedles can not adopt the method administration of injection, the method of first pricking and pasting afterwards can be adopted, namely first cause passage with microneedle keratoderma, then apply with transdermal patch, or strengthen the infiltration of medicine by modes such as electro-ionic osmosis; Also can adopt the administering mode first wrapping and prick afterwards, by medicine first dressing in solid microneedles, then micropin thrusts skin and carries out administration, and dosage places one's entire reliance upon the dressing amount of medicine on micropin.For empty micropin, the general mode administration adopting similar injection, although this injection device more complicated, this administering mode greatly can improve transdermal delivery rates, also can realize successive administration.
From making material, micropin can be divided into [document 4-6] such as silicon micropin, polymer micro needle and metal micro-needles.The excellent performance of silicon materials, cost is low, has critical role in MEMS field, Manufacturing Techniques comparative maturity.Silicon micropin mainly utilizes the technique of isotropism and anisotropic etching to make, and can be made into that different flat solid, empty micropin and isoplanar are solid, empty micropin.But silicon materials have frangible characteristic, if fractureed thrusting in skin process, break-off portion may enter blood circulation system, works the mischief to human body.Polymer micro needle had had in recent years and had been in progress faster.Polymer is as low in costs such as PDMS, PVA, PLGA, and can be made into various isoplanar and different plane micropin, very large polymer also has biocompatibility.In addition, some polymer has biological degradability, leaves in vivo even if micropin fractures, and also can degrade, and need not worry to work the mischief to biology again.The deficiency of polymer micro needle is that the rigidity of most polymers is still inadequate, and hollow polymer micro needle preparation difficulty.Metal has good rigidity, and not easily broken, be good micropin material, some metals such as titanium etc. has good biocompatibility, and metal micro-needle can directly as the microelectrode implanted.At present, many metal materials such as titanium, palladium, nickel, stainless steel, brass etc. can be used for making microneedle array.Titanium mechanical strength is better and have biocompatibility.Palladium is rare metal, and its application is also restricted.The suitable plating of nickel or electroforming, and less expensive, be often selected as lab material.Stainless steel cost compare is low, and price can be accepted comparatively speaking, but stainless steel is not suitable for MEMS technology.Brass is also common materials, but accurately machined condition and cost are too high.The deficiency of present metal micro-needle be reduce costs, to make different plane hollow microneedle more difficult.
Bibliography:
[1]PrausnitzMR.Microneedlesfortransdermaldrugdelivery[J].AdvDrugDelivRev.2004,56(5):581-587.
[2]PrausnitzMR.Microneedlesfortransdermaldrugdelivery[J].AdvDrugDelivRev.2004,56(5):581-587.
[3]MUKERJEEEV,COLLINSSD,ISSEROFFRR,etal.Microneedlearrayfortransdermalbiologicalfluidextractionandinsituanalysis[J].SensActuatorsAphys.2004,114(2-3):508-510.
[4]JINGJI,FRANCISE.H.TAY,JIANMINMIAO.CharacterizationofSiliconIsotropicEtchbyInductivelyCoupledPlasmaEthcerforMicroneedleArrayFabrication[C].InternationalMEMSConference,JournalofPhysics:ConferenceSeries34.2006:1137-1142.
[5]Shyh-ChyiKuo,YukonChou.ANovelPolymerMicroneedleArraysandPDMSMicromoldingTechnique[J].TankangJournalofScienceandEngineering.2004,7(2):95-98.
[6]E.R.Parker,M.P.Rao,K.L.Turner,etal.BulkMicromachinedTitaniumMicroneedles[J].JournalofMicroelectromechanicalSystems.2007,16(2):289-295.
Summary of the invention
The object of the present invention is to provide a kind of method making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip, be difficult to large-scale production, problem that structural strength is low to solve prior art hollow core micropin.
For achieving the above object, the technical solution used in the present invention is as follows:
A preparation method for monocrystalline silicon empty micropin structure, comprises the steps:
(1) provide twin polishing and thickness is (100) type silicon chip of t1, and adopt photoetching process to form at least one first window in the one side of described silicon chip;
(2) adopt dark silicon dry etch process to etch described silicon chip one side, in described first window, Formation Depth is the non-through groove of t2, t2<t1, and removes photoresist;
(3) thermal oxidation is carried out to described silicon chip, thus form silicon oxide layer on the cell wall of the two sides of described silicon chip and described non-through groove;
(4) in described silicon chip one side with in described non-through groove, photoresist is coated with;
(5) carry out photoetching in described silicon chip one side, form photoresist mask array, and make the central point deviation of the central point of wherein photoresist mask and described non-through groove within 100 μm;
(6) at described silicon chip another side coating photoresist, and form Second Window array through photoetching, and make the centre deviation of the center of wherein Second Window and corresponding photoresist mask within 100 μm;
(7) silicon oxide layer described silicon chip two sides not covered in the region of photoresist is removed, then remove the photoresist covered on described silicon chip two sides;
(8) with Silicon Crystal Anisotropic Etching liquid, described silicon chip is corroded, thus polyhedron terrace with edge structure is formed below the photoresist mask of described silicon chip one side, and stop corrosion when corrosion depth t3 is more than or equal to required micropin height and described polyhedron terrace with edge end face dwindles into pinnacle, wherein, t1>2 × t3, t2>t1-t3, forms etching tank at described silicon chip another side simultaneously, and described non-through groove is communicated with described etching tank;
(9) remove silica remaining on described silicon chip, after cleaning, obtain target product.
Formed compared with the method for micropin with adopting isotropic etching in prior art, the present invention adopts the method for anisotropic etch to define to have the different plane hollow microneedle of monocrystalline silicon of eight pyramid needle points, not only technique is simply easy to implement for it, and obtain micropin there is the advantage that structural strength is large, processing cost is low, yield rate is high, uniformity is good, at biomedical sector, there is application prospect.
Accompanying drawing explanation
Fig. 1 is shown as the method step 1 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) ~ 11) process chart that presents, wherein,
1a ~ 1b is shown as the method step 1 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) structural representation that presents;
1c is shown as the method step 2 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) structural representation that presents;
1d is shown as the method step 3 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) structural representation that presents;
1e is shown as the method step 4 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) ~ 6) structural representation that presents;
1f ~ 1g is shown as the method step 7 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) structural representation that presents;
1h ~ 1i is shown as the method step 8 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) ~ 9) structural representation that presents;
1j is shown as the method step 10 making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip of the present invention) ~ 11) structural representation that presents.
Fig. 2 is shown as the process schematic making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention, wherein,
2a is shown as the square mask schematic diagram making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention;
There are two new erosional surface process schematic in mask four corner positions in the monocrystalline silicon that 2b is shown as below the square mask making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention after short time corrosion;
2c be shown as of the present invention on (100) type silicon chip with anisotropic wet corrosion make micropin square mask below monocrystalline silicon certain hour corrosion after upper surface B point and C point adjacent to each other and crossing, form octagonal process schematic;
The monocrystalline silicon that 2d is shown as below the square mask making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention continues the structural representation after corrosion after upper surface forms octagon;
The monocrystalline silicon that 2e is shown as below the square mask making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention continues the cross section structure schematic diagram after corrosion after upper surface forms octagon;
The 2f monocrystalline silicon be shown as below the square mask making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention continues the final structural representation forming eight pyramids of corrosion after upper surface forms octagon;
The 2g monocrystalline silicon be shown as below the square mask making micropin on (100) type silicon chip of anisotropic wet corrosion of the present invention continues the final cross section structure schematic diagram forming eight pyramids of corrosion after upper surface forms octagon.
Fig. 3 a-Fig. 3 b is shown as different corrosion window 112 sizes to the impact of the formed etching tank degree of depth, when corrosion window 112 is too small, at the bottom of etching tank, four sides (all along (111) crystal face) intersect at a point, and the etching tank degree of depth almost no longer increases with the increase of etching time, such as, shown in Fig. 3 b.
Fig. 4 is shown as the cross-sectional view of the different plane hollow microneedle of a kind of monocrystalline silicon of the present invention.
Element numbers illustrates: (100) type silicon chip 101, photoresist 102, poroid dry etching groove 103, silica 104, front etch terrace with edge 105, back side etching tank 106, positive plane hollow microneedle 107, A face square mask 108, A face corrosion terrace with edge lower surface 109, A face corrosion terrace with edge upper surface 110, A face corrosion needle point 111, B face square corrosion window 112.
Detailed description of the invention
Invention broadly provides a kind of at monocrystalline silicon, particularly (100) type silicon chip makes the method for the different plane hollow microneedle structure of monocrystalline silicon.
Among an embodiment of the present invention, the method can comprise: provide one (100) type two throwing silicon chip, in this silicon chip A face with the method coating photoresist of traditional spin coating, makes hole shape window by the method for ultraviolet photolithographic; By dark silicon dry etch process, described silicon chip A face is etched, in hole shape window, form the non-through groove structure of certain depth, remove photoresist; Described silicon chip is carried out thermal oxide, in A face, B face and the certain thickness oxide layer of described groove grown on interior walls; At described silicon chip A face spin coating photoresist, for allowing photoresist form good spreadability in groove, adopt the method that low speed spin coating and high speed spin coating combine in this process; Carry out photoetching in described silicon chip A face, form photoresist mask array, particularly square photoresist mask array; At described silicon chip B face spin coating photoresist, and carry out photoetching, form window array, particularly square window array; The silica do not covered in described silicon chip A face and B face in the region of photoresist is removed, and can adopt the method for wet etching or the method for RIE dry etching, then remove photoresist; Described silicon chip is put into Silicon Crystal Anisotropic Etching liquid corrode; When corrosion depth t3 is more than or equal to required micropin height, stop corrosion, form the pointed cone of band hole in described silicon chip A face; Described silicon chip is put into silica erosion liquid, removes remaining silica on silicon chip, A face obtains the monocrystalline silicon empty micropin being with through hole, and its bottom surface presents octagon-shaped; Described silicon chip is carried out rinsing, removes the anisotropic etchant and silica erosion liquid that may remain.
Further, in a comparatively concrete case study on implementation, the method comprises the following steps:
1) provide one (100) type two throwing silicon chip, thickness is designated as t1, in this silicon chip wherein one side (this face is designated as A face, and the back side is designated as B face) method coating photoresist of traditional spin coating, makes hole shape window by the method for ultraviolet photolithographic;
2) etch described silicon chip A face by dark silicon dry etch process, in hole shape window, form the non-through groove structure of certain depth, the degree of depth is designated as t2, and t2<t1, remove photoresist;
3) described silicon chip is carried out thermal oxide, in A face, B face, and the certain thickness oxide layer of described groove grown on interior walls;
4) at described silicon chip A face spin coating photoresist, in groove, good spreadability is formed for allowing photoresist, adopt the method that low speed spin coating and high speed spin coating combine in this process: first under the condition of 500rad/min, allow adhesive plaster expire silicon chip surface by rotary speed, and fill up described deep trouth, then realize the photoresist coating of desired thickness with the rotating speed of more than 1000rad/min;
5) carry out photoetching in described silicon chip A face, form square photoresist mask array, the central point deviation of foursquare central point and described groove is no more than 100 microns;
6) at described silicon chip B face spin coating photoresist, and carry out photoetching, form square window array, the foursquare center square center deviation corresponding with A face is no more than 100 microns;
7) silica do not covered in described silicon chip A face and B face in the region of photoresist is removed, and can adopt the method for wet etching or the method for RIE dry etching, then remove photoresist;
8) described silicon chip is put into Silicon Crystal Anisotropic Etching liquid to corrode, corrosive liquid includes but not limited to potassium hydroxide solution (KOH), TMAH (TMAH) solution;
9) described silicon chip A face forms polyhedron terrace with edge structure (being greater than 8 faces) in corrosion process below square mask, and change to octahedra terrace with edge gradually, treat that corrosion depth t3 is more than or equal to required micropin height and terrace with edge upper surface dwindles into pinnacle (if hole is at terrace with edge axle center place, then herein criterion can be terrace with edge upper surface and hole circumscribed) time stops corroding, now there is t1>2*t3 in principle, and t2>t1-t3;
10) described silicon chip is put into silica erosion liquid, remove remaining silica on silicon chip;
11) described silicon chip is carried out rinsing, remove residual anisotropic etchant and silica erosion liquid.
One of preferably, step 3) in the ratio of the oxidated layer thickness of growth and required micropin height at more than 1:200.
One of preferably, step 5) described in the ratio of the length of side of square photoresist mask array and required micropin height between 1.5:1 ~ 5:1, be preferably greater than 2.33:1.
One of preferably, step 5) in square mask center and step 2) in the hole slot center superposition that etches.
One of preferably, step 6) described in the ratio of the length of side of square window and required micropin height between 1:1 to 1.5:1, be preferably greater than 1.2:1.
One of preferably, step 6) in square window center and step 2) in the hole slot center superposition that etches.
One of preferably, step 8) described in Silicon Crystal Anisotropic Etching liquid comprise potassium hydroxide solution or TMAH solution, described potassium hydroxide solution comprises temperature at 50 DEG C ~ 95 DEG C, and concentration is in the KOH solution of 30 ~ 50wt%.
Comparatively speaking, the silicon micropin that at present conventional isotropic etching is formed presents arcuate shape due to side cross-section, and mechanical strength is low, and processing uniformity is poor, and the back side does not have groove structure, and therefore hole lengths is larger, and easily generation blocking causes inefficacy; And monocrystalline silicon provided by the invention different plane hollow microneedle side cross-section is triangle (or trapezoidal), there is the advantages such as structural strength is large, processing cost is low, yield rate is high, uniformity is good, and there is the groove of certain depth at the back side, reduce the length of hole, and increase and can carry out medicine carrying in groove, increase medicine carrying dosage, at biomedical sector, there is application prospect.
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to Fig. 1 ~ Fig. 2, embodiment provides a kind of method making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip, the method according to the height of the different plane hollow microneedle structure of aimed single crystal silicon, calculate the form parameter of the A face etching mask 108 preset and the degree of depth to the dark silicon dry etching of silicon chip 101 in etching window 103, thus control corresponding technological parameter, the different plane hollow microneedle structure of monocrystalline silicon of realize target shape.
Fig. 2 is shown as the process schematic making the different plane microneedle configuration of monocrystalline silicon on (100) type silicon chip.As shown in Figure 2 a, silicon chip 101 makes square etching mask 108 by the patterned method of silica, and its length of side is d
a; As shown in Figure 2 b, described silicon chip is placed in 60 DEG C, the KOH solution of 48wt% carries out anisotropic wet corrosion, through shorter etching time, monocrystalline silicon below square mask and the new erosional surface of certain two of mask four each angulations in drift angle place, and other position forms the erosional surface along (111) crystal face below mask, monocrystalline silicon below described mask forms the terrace with edge structure with 12 faces, and its degree of depth equals this corrosive liquid and (is designated as to the corrosion rate of (100) crystal face and v) is multiplied by etching time and (is designated as t); As shown in Figure 2 c, described silicon chip 101 is continued corrosion, the B point of monocrystalline silicon upper surface 110 and C point intersect, and upper surface 110 and the lower surface 109 of terrace with edge structure now form eight-sided formation, wherein, the diagonal angle of eight-sided formation is equal, adjacent drift angle is respectively 143 ° ± 5 ° and 125 ° ± 5 °, in being staggered, if ∠ 1 is 143 ° ± 5 °, then ∠ 2 is 125 ° ± 5 °, by that analogy; As shown in Figure 2 d, described silicon chip 101 is continued corrosion, each drift angle of monocrystalline silicon upper surface 110 and lower surface 109 remains unchanged, but the length of side reduces gradually, and its cross sectional shape as shown in Figure 2 e; As shown in figure 2f, described silicon chip 101 is continued corrosion, monocrystalline silicon upper surface 110 length of side is reduced to 0 gradually, and form pinnacle structure 111, lower surface keeps octagonal shape invariance, and now former eight terrace with edge structures become eight pyramidal structures.
The eight pyramidal structure height t 2 that can be obtained needed for final corrosion by above-mentioned corrosion process calculate designed square mask parameter, implementation step is as follows: the square silicon oxide masking film 108 1) making any length of side on silicon chip 101, described silicon chip 101 is placed in the KOH solution (temperature of actual use, concentration is known) in corrode, after corrosion after a while, silicon chip 101 is taken out, the distance l during this period of time between square mask summit D to monocrystalline silicon upper surface summit A is measured by the method for microscopic observation, terrace with edge height h is measured again with step instrument, according to formula:
The minimum length of side d of square mask 108 can be calculated
a.
Because the existing maximum depth-to-width ratio reached based on the etching energy of dark silicon etching process to cavernous structure 103 of BOSCH technique is about about 20:1, when poroid groove structure 103 degree of depth therefore designed in micropin in the present embodiment is t2, diameter r is not less than t2/20.
Fig. 3 a-3b is shown as different corrosion window 112 sizes to the impact of the formed etching tank degree of depth, when corrosion window 112 is too small, at the bottom of etching tank, four sides (all along (111) crystal face) intersect at a point, and the etching tank degree of depth almost no longer increases with the increase of etching time, as shown in Figure 3 b.For the degree of depth making the corrosion depth of described silicon chip 101 back surface corrosion window reach at least t2, the minimum length of side d of described silicon chip 101 back side square corrosion window 112
bcan be determined by following formula:
d
B＝2·t
2·tg36°+r。(2)
According to above-mentioned design considerations, the invention provides a specific embodiment, be highly 150 microns to make, aperture is the monocrystalline silicon empty micropin of 20 microns.In the present embodiment, temperature is adopted to be 60 DEG C, concentration is that the KOH solution of 48wt% is as Silicon Crystal Anisotropic Etching liquid, needed for the A face calculating described silicon chip 101 according to the characteristic of this corrosive liquid in conjunction with formula (1), the length of side of square mask is 350 microns, the minimum length of side of B face square corrosion window is 240 microns, makes corresponding reticle pattern thus.As shown in Fig. 1 a ~ b, first carry out step 1): one (100) type two throwing silicon chip is provided, thickness is adopted to be the silicon chip of 500 microns in the present embodiment, in this silicon chip A face with the method coating photoresist 102 of traditional spin coating, rubberization thickness is 10 microns, makes hole shape window by the method for ultraviolet photolithographic; As illustrated in figure 1 c, then carry out step 2): etch described silicon chip A face by dark silicon dry etch process, in hole shape window, Formation Depth is the poroid groove structure 103 of 370 microns, removes photoresist 102; As shown in Figure 1 d, then carry out step 3): described silicon chip is carried out thermal oxide, and in A face, B face, and described groove grown on interior walls thickness is the oxide layer 104 of 2 microns; As shown in fig. le, then carry out step 4) ~ 6), at described silicon chip A face spin coating photoresist 102, in groove, good spreadability is formed for allowing photoresist, adopt the method that low speed spin coating and high speed spin coating combine in this process: first under the condition of 500rad/min, allow adhesive plaster expire silicon chip surface by rotary speed, and fill up described deep trouth, then realize with the rotating speed of 3000rad/min the photoresist coating that thickness is about 1.5 microns; Carry out photoetching in described silicon chip A face, form square photoresist mask 108, foursquare central point and step 2) in the poroid groove center that etches overlap; At described silicon chip B face spin coating photoresist about 1.5 microns, and carry out photoetching, form square window 112, foursquare central point and step 2) middle poroid groove 103 center superposition etched; As shown in Fig. 1 f ~ g, then carry out step 7): the method described silicon chip A face and B face not being covered the silica 104 BOE solution wet etching in the region of photoresist is removed, and then removes photoresist 102 by the method for acetone ultrasonic cleaning; As shown in Fig. 1 h ~ i, then carry out step 8) ~ 9): described silicon chip is put into 60 DEG C, the KOH solution of 48wt% concentration corrodes, when corrosion depth reaches 150 microns, described silicon chip A face terrace with edge upper surface 110 is all taken by poroid groove 103 top, exposes a bit of silica bottom poroid groove 103 (about 20 microns high) inwall bottom the B face etching tank of described silicon chip; As shown in fig. ij, finally carry out step 10) ~ 11): described silicon chip is put into BOE solution, remove remaining silica 104 on silicon chip, described silicon chip 101 is carried out rinsing with the concentrated sulfuric acid solution of 120 DEG C, remove residual KOH corrosive liquid, finally use rinsed with deionized water, remove other impurity on described silicon chip, obtaining required height is 150 microns, and center bore is the different plane hollow microneedle structure 107 of monocrystalline silicon of 20 microns.Monocrystalline silicon provided by the invention different plane hollow microneedle side cross-section is triangle (or trapezoidal), there is the advantage that structural strength is large, processing cost is low, yield rate is high, uniformity is good, and there is the groove of certain depth at the back side, reduce the length of hole, and increase and can carry out medicine carrying in groove, increase medicine carrying dosage, at biomedical sector, there is application prospect.
In sum, the invention provides a kind of method making the different plane hollow microneedle structure of monocrystalline silicon on (100) type silicon chip, comprise step: provide one (100) type two throwing silicon chip, in this silicon chip A face with the method coating photoresist of traditional spin coating, make hole shape window by the method for ultraviolet photolithographic; By dark silicon dry etch process, described silicon chip A face is etched, in hole shape window, form the non-through groove structure of certain depth, remove photoresist; Described silicon chip is carried out thermal oxide, in A face, B face, and the certain thickness oxide layer of described groove grown on interior walls; At described silicon chip A face spin coating photoresist, for allowing photoresist form good spreadability in groove, adopt the method that low speed spin coating and high speed spin coating combine in this process; Carry out photoetching in described silicon chip A face, form square photoresist mask array; At described silicon chip B face spin coating photoresist, and carry out photoetching, form square window array; The silica do not covered in described silicon chip A face and B face in the region of photoresist is removed, and can adopt the method for wet etching or the method for RIE dry etching, then remove photoresist; Described silicon chip is put into Silicon Crystal Anisotropic Etching liquid corrode; When corrosion depth t3 is more than or equal to required micropin height, stop corrosion, form the pointed cone of band hole in described silicon chip A face; Described silicon chip is put into silica erosion liquid, removes remaining silica on silicon chip, A face obtains the monocrystalline silicon empty micropin being with through hole, and its bottom surface presents octagon-shaped; Described silicon chip is carried out rinsing, removes residual anisotropic etchant and silica erosion liquid.The different plane hollow microneedle of the monocrystalline silicon that the present invention proposes adopts the method for anisotropic etch to form eight pyramid needle points, and the micropin comparing isotropic etching formation conventional at present has the advantage that structural strength is large, processing cost is low, yield rate is high, uniformity is good.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Thus, it will be appreciated by those skilled in the art that above-described embodiment only illustrative principle of the present invention and effect thereof, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (12)
1. a preparation method for monocrystalline silicon empty micropin structure, is characterized in that comprising the steps:
(1) provide twin polishing and thickness is (100) type silicon chip of t1, and adopt photoetching process to form at least one first window in the one side of described silicon chip;
(2) adopt dark silicon dry etch process to etch described silicon chip one side, in described first window, Formation Depth is the non-through groove of t2, t2<t1, and removes photoresist;
(3) thermal oxidation is carried out to described silicon chip, thus form silicon oxide layer on the cell wall of the two sides of described silicon chip and described non-through groove;
(4) in described silicon chip one side and described non-through groove, photoresist is coated with;
(5) photoetching is carried out to described silicon chip one side, form photoresist mask array, and make the central point deviation of the central point of wherein photoresist mask and described non-through groove within 100 μm;
(6) at described silicon chip another side coating photoresist, and form Second Window array through photoetching, and make the centre deviation of the center of wherein Second Window and corresponding photoresist mask within 100 μm;
(7) silicon oxide layer described silicon chip two sides not covered in the region of photoresist is removed, then remove the photoresist covered on described silicon chip two sides;
(8) with Silicon Crystal Anisotropic Etching liquid, described silicon chip is corroded, thus polyhedron terrace with edge structure is formed below the photoresist mask of described silicon chip one side, and stop corrosion when corrosion depth t3 is more than or equal to required micropin height and described polyhedron terrace with edge end face dwindles into pinnacle, wherein, t1>2 × t3, t2>t1-t3, forms etching tank at described silicon chip another side simultaneously, and described non-through groove is communicated with described etching tank;
(9) remove silica remaining on described silicon chip, after cleaning, obtain target product.
2. the preparation method of monocrystalline silicon empty micropin structure according to claim 1, is characterized in that, the ratio of the silicon oxide layer thickness grown in step 3) and required micropin height is at more than 1:200.
3. the preparation method of the monocrystalline silicon empty micropin structure according to any one of claim 1-2, it is characterized in that, step 4) comprises: first adopt rotary speed to fill photoresist in the low speed spin coating mode of below 500rad/min at described silicon chip surface, and fill up described non-through groove, then adopt rotary speed on described silicon chip surface, to be coated with the photoresist of desired thickness in the high speed spin coating mode of more than 1000rad/min again.
4. the preparation method of the monocrystalline silicon empty micropin structure according to any one of claim 1-3, is characterized in that, the photoresist mask array described in step 5) is square photoresist mask array.
5. the preparation method of monocrystalline silicon empty micropin structure according to claim 4, is characterized in that, the central point of the mask of photoresist described in step 5) and the point coincides of described non-through groove.
6. the preparation method of monocrystalline silicon empty micropin structure according to claim 4, is characterized in that, the length of side of described square photoresist mask array and the ratio of required micropin height are between 1.5:1 ~ 5:1.
7. the preparation method of the monocrystalline silicon empty micropin structure according to any one of claim 1-6, is characterized in that described Second Window adopts square window.
8. the preparation method of monocrystalline silicon empty micropin structure according to claim 7, is characterized in that the ratio of the length of side of described square window and required micropin height is between 1:1 to 1.5:1.
9. the preparation method of monocrystalline silicon empty micropin structure according to claim 7, is characterized in that the center superposition of described square window center and described non-through groove.
10. the preparation method of the monocrystalline silicon empty micropin structure according to any one of claim 1-9, the method that it is characterized in that removing in step 7) silica comprises method or the RIE dry etching method of wet etching.
The preparation method of 11. monocrystalline silicon empty micropin structures according to any one of claim 1-10, it is characterized in that, step 8) comprises: corrode described silicon chip with Silicon Crystal Anisotropic Etching liquid, thus the polyhedron terrace with edge structure being greater than 8 is formed below the photoresist mask of described silicon chip one side, and change to octahedra terrace with edge gradually, when corrosion depth t3 is more than or equal to required micropin height and terrace with edge upper surface dwindles into pinnacle, stop corrosion.
The preparation method of 12. monocrystalline silicon empty micropin structures according to any one of claim 1-11, it is characterized in that, the liquid of Silicon Crystal Anisotropic Etching described in step 8) comprises potassium hydroxide solution or TMAH solution, described potassium hydroxide solution comprises temperature at 50 DEG C ~ 95 DEG C, and concentration is in the KOH solution of 30 ~ 50wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410253151.8A CN105217565B (en) | 2014-06-09 | 2014-06-09 | Manufacturing method of single crystal silicon hollow micro-needle structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410253151.8A CN105217565B (en) | 2014-06-09 | 2014-06-09 | Manufacturing method of single crystal silicon hollow micro-needle structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105217565A true CN105217565A (en) | 2016-01-06 |
| CN105217565B CN105217565B (en) | 2017-01-11 |
Family
ID=54986923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410253151.8A Active CN105217565B (en) | 2014-06-09 | 2014-06-09 | Manufacturing method of single crystal silicon hollow micro-needle structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105217565B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106426729A (en) * | 2016-11-09 | 2017-02-22 | 江苏信息职业技术学院 | Semiconductor microneedle assembly based on gene therapy, manufacturing method and manufacturing mold |
| CN106809802A (en) * | 2017-03-01 | 2017-06-09 | 中国电子科技集团公司第三十八研究所 | The preparation method of large-area metal nanometer pinpoint array in a kind of flexible substrate |
| CN108883263A (en) * | 2016-03-31 | 2018-11-23 | 花王株式会社 | Fine hollow bumps utensil |
| CN109545894A (en) * | 2018-11-20 | 2019-03-29 | 哈尔滨工业大学 | A kind of preparation method of eight prismatic table shape patterned silicon substrates |
| CN109795978A (en) * | 2018-12-26 | 2019-05-24 | 华中科技大学 | A kind of micro hollow silicon needle tubing array and preparation method thereof |
| CN109893753A (en) * | 2019-04-08 | 2019-06-18 | 苏州泽矽能电子科技有限公司 | A kind of monocrystalline silicon high throughput microneedle configuration |
| CN110002393A (en) * | 2019-04-04 | 2019-07-12 | 中国科学院微电子研究所 | The preparation method of method for selective etching and nanometer pinpoint structure |
| CN110711312A (en) * | 2019-11-07 | 2020-01-21 | 河南大学 | Micro-electromechanical system based strong permeation-promoting transdermal drug release micro-system and manufacturing method thereof |
| CN110812686A (en) * | 2019-11-07 | 2020-02-21 | 河南大学 | Micro-processing technology for manufacturing microneedle array and microneedles |
| CN113209466A (en) * | 2021-05-11 | 2021-08-06 | 苏州揽芯微纳科技有限公司 | Monocrystalline silicon hollow microneedle structure and manufacturing method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6406638B1 (en) * | 2000-01-06 | 2002-06-18 | The Regents Of The University Of California | Method of forming vertical, hollow needles within a semiconductor substrate, and needles formed thereby |
| CN1526454A (en) * | 2003-03-06 | 2004-09-08 | 财团法人工业技术研究所 | Manufacture of micro syringe array |
| CN101332327A (en) * | 2008-08-06 | 2008-12-31 | 清华大学 | Micro hollow silicon needle and preparation method thereof |
| CN101342404B (en) * | 2008-08-28 | 2010-04-14 | 上海交通大学 | Method for manufacturing different-plane metal hollow fine needle for transdermal drug administration |
| CN102530848A (en) * | 2012-03-06 | 2012-07-04 | 大连理工大学 | Method for manufacturing mosquito-mouth-imitated hollow microneedle array |
| JP2013252580A (en) * | 2012-06-05 | 2013-12-19 | Toppan Printing Co Ltd | Method for manufacturing microneedle structure |
-
2014
- 2014-06-09 CN CN201410253151.8A patent/CN105217565B/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108883263A (en) * | 2016-03-31 | 2018-11-23 | 花王株式会社 | Fine hollow bumps utensil |
| US11129974B2 (en) | 2016-03-31 | 2021-09-28 | Kao Corporation | Fine hollow protrusion implement |
| CN106426729A (en) * | 2016-11-09 | 2017-02-22 | 江苏信息职业技术学院 | Semiconductor microneedle assembly based on gene therapy, manufacturing method and manufacturing mold |
| CN106809802A (en) * | 2017-03-01 | 2017-06-09 | 中国电子科技集团公司第三十八研究所 | The preparation method of large-area metal nanometer pinpoint array in a kind of flexible substrate |
| CN109545894B (en) * | 2018-11-20 | 2020-08-25 | 哈尔滨工业大学 | Preparation method of inverted eight-edge frustum-shaped patterned silicon substrate |
| CN109545894A (en) * | 2018-11-20 | 2019-03-29 | 哈尔滨工业大学 | A kind of preparation method of eight prismatic table shape patterned silicon substrates |
| CN109795978A (en) * | 2018-12-26 | 2019-05-24 | 华中科技大学 | A kind of micro hollow silicon needle tubing array and preparation method thereof |
| CN110002393A (en) * | 2019-04-04 | 2019-07-12 | 中国科学院微电子研究所 | The preparation method of method for selective etching and nanometer pinpoint structure |
| CN109893753A (en) * | 2019-04-08 | 2019-06-18 | 苏州泽矽能电子科技有限公司 | A kind of monocrystalline silicon high throughput microneedle configuration |
| CN110711312A (en) * | 2019-11-07 | 2020-01-21 | 河南大学 | Micro-electromechanical system based strong permeation-promoting transdermal drug release micro-system and manufacturing method thereof |
| CN110812686A (en) * | 2019-11-07 | 2020-02-21 | 河南大学 | Micro-processing technology for manufacturing microneedle array and microneedles |
| CN110812686B (en) * | 2019-11-07 | 2021-07-30 | 河南大学 | Micro-processing technology for manufacturing microneedle array and microneedles |
| CN110711312B (en) * | 2019-11-07 | 2021-07-30 | 河南大学 | Micro-electromechanical system based strong permeation-promoting transdermal drug release micro-system and manufacturing method thereof |
| CN113209466A (en) * | 2021-05-11 | 2021-08-06 | 苏州揽芯微纳科技有限公司 | Monocrystalline silicon hollow microneedle structure and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105217565B (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105217565A (en) | A kind of preparation method of monocrystalline silicon empty micropin structure | |
| US6558361B1 (en) | Systems and methods for the transport of fluids through a biological barrier and production techniques for such systems | |
| US7285113B2 (en) | Systems and methods for the transport of fluids through a biological barrier and production techniques for such systems | |
| Stoeber et al. | Arrays of hollow out-of-plane microneedles for drug delivery | |
| Gardeniers et al. | Silicon micromachined hollow microneedles for transdermal liquid transport | |
| Moon et al. | Fabrication of microneedle array using LIGA and hot embossing process | |
| CN101244303A (en) | Miniature solid or hollow silicon needle, silicon needle array and preparing method thereof | |
| CN101342404B (en) | Method for manufacturing different-plane metal hollow fine needle for transdermal drug administration | |
| CN100460028C (en) | Miniature needle array for medicine transmission and its making process | |
| US20090093776A1 (en) | 3d solid or hollow silicon microneedle and microknife with "-" shape structure | |
| JP2002517300A (en) | Microneedle devices and methods of manufacture and uses thereof | |
| CN109893753A (en) | A kind of monocrystalline silicon high throughput microneedle configuration | |
| Ji et al. | Microfabricated silicon microneedle array for transdermal drug delivery | |
| CN106422044A (en) | Hafnium oxide hollow microneedle based on silicon substrate and preparation method thereof | |
| Shikida et al. | Fabrication of a hollow needle structure by dicing, wet etching and metal deposition | |
| US9919916B2 (en) | Manufacture of microneedles | |
| Jurčíček et al. | Design and fabrication of hollow out‐of‐plane silicon microneedles | |
| CN101862503B (en) | Method for preparing off-plane hollow microneedle array for use in transdermal medicament administration | |
| Lee | Fabrication of microneedle array using inclined LIGA process | |
| CN209917068U (en) | Monocrystalline silicon high-flux microneedle structure | |
| CN104587567B (en) | A kind of preparation method of micro hollow silicon needle | |
| WO2001066065A2 (en) | Systems and methods for fluid transport through dermal barriers | |
| Imaeda et al. | Sharp tip-separable microneedle device for trans-dermal drug delivery systems | |
| CN110279935B (en) | Prismatic silicon microneedle and preparation method thereof | |
| CN110812686A (en) | Micro-processing technology for manufacturing microneedle array and microneedles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |