CN104190484A - Preparation method of chip unit suitable for biomolecule detection - Google Patents
Preparation method of chip unit suitable for biomolecule detection Download PDFInfo
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- CN104190484A CN104190484A CN201410470410.2A CN201410470410A CN104190484A CN 104190484 A CN104190484 A CN 104190484A CN 201410470410 A CN201410470410 A CN 201410470410A CN 104190484 A CN104190484 A CN 104190484A
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Abstract
The invention discloses a preparation method of a chip unit suitable for the biomolecule detection. The preparation method comprises the steps of depositing an electric heating insulating material and a base material on a substrate; making a graph by using photoetching and dry etching methods and taking the graph as a base of a side wall; depositing a side wall material; forming the side wall, whose height and width are both in nanoscale, by dry back-etching; removing the base of the side wall through a wet corrosion method; adopting processes of photoetching or electron beam lithography and thin-film deposition and peeling to build a metal layer used for making an electrode on the side wall; preparing an insulating material layer through the thin-film deposition process; cutting off metal connection on the two sides of the side wall while polishing the surface by using a chemico-mechanical polishing method; removing the residual side wall material by using the wet corrosion method to form a nano fluid flow passage; bonding wafers to cap and thinning a capping wafer; and forming holes in the two ends of the passage, forming holes in metals on the two sides of the passage, and leading the electrode out. The preparation method breaks through the limitation of photoetching resolution ratio, improves the compatibility of the chip unit and a CMOS (complementary metal oxide semiconductor) process, and improves the preparation efficiency of the chip unit used for biomolecule detection.
Description
Technical field
The present invention relates to micro-nano technical field, relate in particular to a kind of preparation method who is suitable for the chip unit of biomolecule detection.
Background technology
Receiving fluid passage especially has a wide range of applications at micro-nano biological field in nanometer technique field.The chip unit that is suitable for biomolecule detection that fluid passage combines with electrode and form will be received, can realize DNA/RNA, protein, medicine, drugs and amino acid etc. are detected to analysis, be applied in the fields such as gene sequencing, drug screening, protein science, clinical diagnosis.In order to realize this chip unit that is suitable for biomolecule detection, first must obtain width is the nano level fluid passage of receiving, and then in passage, makes the electrode that spacing is less.But, at width, be that nano level receiving in fluid passage prepared the electrode that spacing is less, there is very large technical difficulty; Enable to realize, also have the defect that poor repeatability and cost are high.Therefore, how to realize receive fluid passage and electrode be effectively combined into we research important directions.
At present, the preparation method of nanostructured mainly contains: photoetching, electron beam lithography, focused-ion-beam lithography, micro-contact printing, electrochemical method and electromigration method etc.But optical lithography method is subject to optical wavelength restriction, the limit of etching, in micron dimension, is difficult to reach nanometer scale; The method cycle of micro-contact printing, electron beam lithography and focused-ion-beam lithography grows up to this height; Electrochemistry and electromigration method reliability of technology are lower, may cause incompatible with CMOS technique.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method who is suitable for the chip unit of biomolecule detection, simple and cost is lower, can break through the compatibility of photoetching resolution restriction and raising chip unit and CMOS technique, and improve the preparation efficiency of the chip unit that is suitable for biomolecule detection.
For achieving the above object, the present invention takes following technical scheme:
A preparation method who is suitable for the chip unit of biomolecule detection, comprises the steps:
(1), at the erosion-resisting electric insulating material layer of Grown one deck, then on electric insulating material layer, deposit one deck substrate material layer;
(2) by the method for photoetching and dry etching, remove four limits of substrate material layer, form figure as the substrate of preparing side wall;
(3) at the upper surface of electric insulating material layer and outer surface deposit one deck spacer material layer of substrate material layer;
(4) adopt dry back to carve, remove the spacer material layer of substrate material layer upper surface and the part spacer material layer of electric insulating material layer upper surface, form the spacer material layer that height and width are nano-scale;
(5) adopt the method for wet etching to remove substrate material layer, only retain the spacer material layer of nano-scale;
(6) adopt photoetching or beamwriter lithography+thin-film deposition+stripping technology on a limit of spacer material layer, to cost an erosion-resisting metal level of making electrode;
(7) adopting film deposition art to prepare one deck at step (6) gained unit upper surface makes and receives the anticorrosive insulation material layer of fluid passage;
(8) adopt the upper surface of the method polishing step gained unit of chemically mechanical polishing CMP, cut off the connection of the metal level of spacer material layer both sides simultaneously, in described polishing process, the metal level at spacer material layer top is thrown and broken, and retain the metal level on electric heating insulating barrier;
(9) adopting wet etching method to remove remaining spacer material layer forms and receives fluid passage;
(10) adopt the mode of bonding chip, at step (9) the gained unit upper surface preparation wafer that binds, will receive fluid passage binds, and then attenuate binds the thickness of wafer to several microns of-tens micron dimensions;
(11) receiving the perforate of two ends, fluid passage, and obtaining from receiving extraction electrode the metal level of passage both sides, fluid passage the chip unit that is suitable for biomolecule detection.
Further, step (7) adopts film deposition art to prepare lamination that structure is followed successively by SiO2, SiN and SiO2 from top to bottom and receives the anticorrosive insulation material layer of fluid passage as making, wherein SiN is as the cutoff layer of step (8) chemically mechanical polishing CMP method, and step (8) uses chemically mechanical polishing CMP method polishing step (7) gained unit upper surface to the SiN cutoff layer of anticorrosive insulation material layer.
Further, the width of fluid passage received is 5-200nm, and be highly greater than institute's deposit metal level thickness and be less than the height of spacer material layer.
Further, electric insulating material, substrate material layer, spacer material layer and corrosion-resistant material layer are oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide.
Further, electric insulating material layer is silicon nitride or SiO2; Described substrate material layer is SiO2, silicon nitride or polysilicon; Described spacer material layer is SiO2, silicon nitride or polysilicon; Described noncorroding metal layer is tungsten, nickel, copper, silver, gold or platinum; Described anticorrosive insulation material layer is SiO2 or silicon nitride.
Further, substrate is semiconductive material substrate or insulative material substrate; Described semiconductive material substrate is selected silicon chip or SOI sheet; Described insulative material substrate is selected SiO
2or glass.
Further, the preferred 20-2000nm of the thickness of substrate material layer; The preferred 5-200nm of width of the side wall that described spacer material layer forms.
Further, growth electric insulating material, deposit substrate material layer in step (1), step (3) deposit spacer material layer and step (7) deposit corrosion-resistant material layer adopt respectively a kind of realization in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process; Described step (6) noncorroding metal layer adopts a kind of preparation the in sputtering method, evaporation and CVD method.
The corrosive liquid using when further, spacer material layer is removed substrate material layer to step (5) is middle has corrosion resistance; The corrosive liquid that described metal level is used while removing spacer material layer to step (9) is middle has corrosion resistance; The corrosive liquid that described corrosion-resistant material layer is used while removing spacer material layer for step (9) is middle has corrosion resistance.
Further, step (5) wet etching method employing corrosive liquid is HF acid, TMAH solution or hot SPA; It is HF acid, TMAH solution or hot SPA that described step (9) wet etching method adopts corrosive liquid.
Beneficial effect: (1) provided by the invention is suitable for the method for preparation of the chip unit of biomolecule detection, adopt thin-film technique, lithography stripping technique, photoetching dry etch process, wet-etching technology and side wall technique to make, what adopt is all traditional silicon planar technology, has natural compatibility with CMOS technique;
(2) the present invention only need to just can realize the chip unit that possesses nano-scale on a large scale with optics etching condition, avoided use electron beam exposure (EBL), the technology such as FIB exposure (FIB), thereby broken through the restriction of optical resolution, reduce cost, improved the preparation efficiency of chip unit.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the chip unit that is suitable for biomolecule detection provided by the invention flow chart;
Fig. 2 is the structural representation of step (1), step (2) made chip unit.
Fig. 3 is the structural representation of step (3) made chip unit.
Fig. 4 is the structural representation of step (4) made chip unit.
Fig. 5 is the structural representation of step (5) made chip unit.
Fig. 6 is the structural representation of step (6) made chip unit.
Fig. 7 is the structural representation of step (7) made chip unit.
Fig. 8 is the structural representation of step (8) made chip unit.
Fig. 9 is the structural representation of step (9) made chip unit.
Figure 10 is the structural representation of step (10) made chip unit.
Figure 11 is the structural representation of step (11) made chip unit.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
As shown in Figure 1, a kind of preparation method who is suitable for the chip unit of biomolecule detection provided by the invention, comprises the steps:
(1) as shown in Figure 2, the erosion-resisting electric insulating material layer 102 of the one deck of growing on substrate 101 then deposits one deck substrate material layer 103 on electric insulating material layer 102.
Wherein, substrate 101 is semiconductive material substrate or insulative material substrate, and semiconductive material substrate can be selected silicon chip or SOI sheet, and insulative material substrate can be selected SiO
2or glass; Electric insulating material 102, can be oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide, preferred nitrogen SiClx of the present invention or SiO2; One deck electric insulating material 102 of growing on substrate 101, can adopt a kind of realization in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process; Electric insulating material 102, for wet method in step (5) remove substrate material layer 103 and after the equal tool corrosion resistance of corrosive liquid used when wet method is removed spacer material layer 104 in the step (9) chatted; Substrate material layer 103, can be oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide, the preferred SiO2 of the present invention, silicon nitride or polysilicon, the preferred 20-2000nm of thickness of substrate material layer 103; Deposit one deck substrate material layer 103, can adopt a kind of realization in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process.
(2) by the method for photoetching and dry etching, remove four limits of substrate material layer 103, form figure as the substrate of preparing side wall, as shown in Figure 2.
(3) as shown in Figure 3, at the upper surface of electric insulating material layer 102 and outer surface deposit one deck spacer material layer 104 of substrate material layer 103.
Wherein spacer material layer 104, can be oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide, the preferred SiO2 of the present invention, silicon nitride or polysilicon, the preferred 5-200nm of width of spacer material layer 104; Deposit one deck spacer material layer 104, can adopt a kind of realization in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process; Spacer material layer 104, for after the corrosive liquid that uses while removing substrate material layer 103 in the step (5) chatted there is corrosion resistance.
(4) as shown in Figure 4, adopt dry back to carve, remove the spacer material layer 104 of substrate material layer 103 upper surfaces and the part spacer material layer 104 of electric insulating material layer 102 upper surface, form the spacer material layer 104 that height and width are nano-scale.
(5) as shown in Figure 5, by the method for wet etching, remove substrate material layer 103, only retain the spacer material layer 104 of nano-scale; Corrosive liquid wherein can be a kind of in HF acid, TMAH solution and hot SPA etc.
(6) on a limit of spacer material layer 104, (optionally wherein a limit) costs an erosion-resisting metal level 105 of making electrode as shown in Figure 6, then with photoetching or beamwriter lithography+thin-film deposition+stripping technology.
Wherein, erosion-resisting metal level 105, the corrosive liquid using when removing spacer material layer 104 in step 9 has corrosion resistance; Erosion-resisting metal level 105 can be any in tungsten, nickel, copper, silver, gold and platinum; Erosion-resisting metal level 105 can be a kind of preparation theing adopt in sputtering method, evaporation and CVD method.
(7) as shown in Figure 7, adopting film deposition art to prepare one deck at step (6) gained unit upper surface makes and receives the anticorrosive insulation material layer 106 of fluid passage.
Corrosion-resistant material layer 106, the corrosive liquid using when removing spacer material layer 104 in step 9 has corrosion resistance; Corrosion-resistant material layer 106, can be oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide, the preferred SiO2 of the present invention or silicon nitride; Deposit corrosion-resistant material layer 106 can be a kind of realization theing adopt in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process.
(8) as shown in Figure 8, upper surface with method polishing step (7) the gained unit of chemically mechanical polishing (CMP), cut off the connection of the metal 105 of side wall 104 both sides simultaneously, in described polishing process, the metal at side wall top 105 must be thrown and broken, and can not throw the metal 105 on electric heating insulating barrier 102.
(9) as shown in Figure 9, with wet etching method, removing remaining spacer material layer 104 forms and receives fluid passage 107, corrosive liquid wherein can be a kind of in HF acid, TMAH solution, hot SPA etc., wherein receive the preferred 5-200nm of width of fluid passage 107, and be highly greater than institute's deposit metal 105 thickness and be less than the height of side wall 104.
(10) as shown in figure 10, by the mode of bonding chip, at step (9) the gained unit upper surface preparation wafer 108 that binds, will receive fluid passage 107 binds, and then attenuate binds the thickness of wafer 108 to several microns of-tens micron dimensions.
(11) as shown in figure 11, receive fluid passage 107 two ends perforates, and can form the chip unit that is suitable for biomolecule detection receiving extraction electrode on the metal 105 of 107 passage both sides, fluid passage.
In order to further illustrate the concrete preparation process of the chip unit of biomolecule detection, as a kind of specific embodiment of the present invention, the present invention includes following steps:
(1) adopt the semiconductors such as monocrystalline silicon piece, SOI silicon-on-insulator or insulating materials as substrate 101;
(2) adopt thin film preparation process, on substrate, prepare 200nm silicon nitride as electric heating insulating barrier 102 and 450nm polysilicon as substrate material layer 103;
(3) by the method for photoetching and dry etching, remove four limits of substrate material layer 103, form figure as the substrate of preparing side wall;
(4) at this above electric insulating material layer 102 and surface of substrate material layer 103 and side deposit 200nm SiO2 as spacer material layer 104;
(5) adopt dry back to carve, remove substrate material layer 103 upper surfaces with spacer material layers 104 electric insulating material layer 102 surface, will form the SiO2 side wall of high 450nm and wide 88nm;
(6) with constant temperature TMAH TMAH solution, float sidewall substrate 103 (constant temperature TMAH solution is very high to the etching selection ratio of underlayer nitriding silicon and side wall silica), the temperature constant of TMAH solution, in 70 ℃, only retains the side wall of nano-scale;
(7) adopt photoetching or beamwriter lithography+thin-film deposition+stripping technology on a limit of this spacer material layer 104, to cost a tungsten metal level 105 of making electrode, metal thickness is 50nm;
(8) with film deposition art PECVD, preparing structure is again that the lamination of 200nm SiO2/100nm SiN/200nm SiO2 is received the anticorrosive insulation material layer 106 of fluid passage as making, and wherein SiN is as the cutoff layer of CMP technique;
(9) with method polished surface to the SiN cutoff layer of chemically mechanical polishing (CMP), cut off the connection of the metal 105 of side wall 104 both sides simultaneously, then with the buffered HF of dilution, remove remaining spacer material 104 and form and receive fluid passage 107;
(10) use bonding chip mode, will receive fluid passage 107 bind with the wafer 108 that binds, and the wafer 108 that will bind carries out attenuate from the back side, reduced thickness is to several microns of-tens micron dimensions;
(11) last again the perforate of passage two ends and on the metal of passage both sides 105 extraction electrodes can form the chip unit that is suitable for biomolecule detection; the channel width of this chip unit is that 88nm is highly 350nm; electrode spacing is 88nm; and can carry out the preparation of scale, and traditional optical etching can only realize the electrode spacing of micron dimension.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. be suitable for a preparation method for the chip unit of biomolecule detection, it is characterized in that comprising the steps:
(1) at the upper growth of substrate (101) the erosion-resisting electric insulating material layer of one deck (102), then in the upper deposition of electric insulating material layer (102) one deck substrate material layer (103);
(2) by the method for photoetching and dry etching, remove four limits of substrate material layer (103), form figure as the substrate of preparing side wall;
(3) at the upper surface of electric insulating material layer (102) and outer surface deposit one deck spacer material layer (104) of substrate material layer (103);
(4) adopt dry back to carve, remove the spacer material layer (104) of substrate material layer (103) upper surface and the part spacer material layer (104) of electric insulating material layer (102) upper surface, form the spacer material layer (104) that height and width are nano-scale;
(5) adopt the method for wet etching to remove substrate material layer (103), only retain the spacer material layer (104) of nano-scale;
(6) adopt photoetching or beamwriter lithography+thin-film deposition+stripping technology on a limit of spacer material layer (104), to cost an erosion-resisting metal level (105) of making electrode;
(7) adopting film deposition art to prepare one deck at step (6) gained unit upper surface makes and receives the anticorrosive insulation material layer (106) of fluid passage;
(8) adopt the upper surface of method polishing step (7) the gained unit of chemically mechanical polishing CMP, cut off the connection of the metal level (105) of spacer material layer (104) both sides simultaneously, in described polishing process, the metal level (105) at spacer material layer (104) top is thrown and broken, and retain the metal level (105) on electric heating insulating barrier (102);
(9) adopting wet etching method to remove remaining spacer material layer (104) forms and receives fluid passage (107);
(10) adopt the mode of bonding chip, at step (9) the gained unit upper surface preparation wafer (108) that binds, will receive fluid passage (107) binds, and then attenuate binds the thickness of wafer (108) to several microns of-tens micron dimensions;
(11) receiving fluid passage (107) two ends perforate, and obtaining from receiving extraction electrode the metal level (105) of passage both sides, fluid passage (107) chip unit that is suitable for biomolecule detection.
2. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, it is characterized in that: described step (7) adopts film deposition art to prepare lamination that structure is followed successively by SiO2, SiN and SiO2 from top to bottom and receives the anticorrosive insulation material layer (106) of fluid passage as making, wherein SiN is as the cutoff layer of step (8) chemically mechanical polishing CMP method, and step (8) uses chemically mechanical polishing CMP method polishing step (7) gained unit upper surface to the SiN cutoff layer of anticorrosive insulation material layer.
3. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, it is characterized in that: described in to receive the width of fluid passage (107) be 5-200nm, and be highly greater than institute's deposit metal level (105) thickness and be less than the height of spacer material layer (104).
4. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, it is characterized in that: described electric insulating material (102), substrate material layer (103), spacer material layer (104) and corrosion-resistant material layer (106) are oxide, nitride or sulfide, or at least two kinds of mixtures that form in oxide, nitride, sulfide.
5. according to a kind of preparation method who is suitable for the chip unit of biomolecule detection described in claim 1 or 4, it is characterized in that: described electric insulating material layer (102) is silicon nitride or SiO2; Described substrate material layer (103) is SiO2, silicon nitride or polysilicon; Described spacer material layer (104) is SiO2, silicon nitride or polysilicon; Described noncorroding metal layer (105) is tungsten, nickel, copper, silver, gold or platinum; Described anticorrosive insulation material layer (106) is SiO2 or silicon nitride.
6. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, is characterized in that: described substrate (101) is semiconductive material substrate or insulative material substrate; Described semiconductive material substrate is selected silicon chip or SOI sheet; Described insulative material substrate is selected SiO
2or glass.
7. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, is characterized in that: the thickness of described substrate material layer (103) is 20-2000nm; The width of the side wall that described spacer material layer (104) forms is 5-200nm.
8. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, it is characterized in that: growth electric insulating material (102), deposit substrate material layer (103) in described step (1), step (3) deposit spacer material layer (104) and step (7) deposit corrosion-resistant material layer (106) adopt respectively a kind of realization in sputtering method, evaporation, plasmaassisted sedimentation, CVD method, metallo-organic decomposition process, laser assisted sedimentation and thermal oxidation process; Described step (6) noncorroding metal layer (105) adopts a kind of preparation the in sputtering method, evaporation and CVD method.
9. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, is characterized in that: the corrosive liquid that described spacer material layer (104) is used while removing substrate material layer (103) to step (5) is middle has corrosion resistance; The corrosive liquid that described metal level (105) is used while removing spacer material layer (104) to step (9) is middle has corrosion resistance; The corrosive liquid that described corrosion-resistant material layer (106) is used while removing spacer material layer (104) for step (9) is middle has corrosion resistance.
10. a kind of preparation method who is suitable for the chip unit of biomolecule detection according to claim 1, is characterized in that: it is HF acid, TMAH solution or hot SPA that described step (5) wet etching method adopts corrosive liquid; It is HF acid, TMAH solution or hot SPA that described step (9) wet etching method adopts corrosive liquid.
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| WO2019023943A1 (en) * | 2017-08-01 | 2019-02-07 | 深圳华大基因研究院 | Fluidic channel structure device and manufacturing method therefor |
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