阅读说明：本技术 一种石墨烯生物传感器电极及其制备工艺 (Graphene biosensor electrode and preparation process thereof ) 是由 李冠华 颜丹 董青龙 ***华 于 2019-12-17 设计创作，主要内容包括：本发明涉及一种石墨烯生物传感器电极,包括绝缘基体、第一直立石墨烯电极、第一焊盘和第一导电孔,第一导电孔贯穿绝缘基体,第一直立石墨烯电极和第一焊盘分别位于绝缘基体的两侧,第一导电孔上下连通第一直立石墨烯电极和第一焊盘,绝缘基体为陶瓷基。绝缘基体设置成陶瓷基体,能够满足多次重复使用的要求,设置直立石墨烯电极,直立石墨烯电极的表面积大,对电的灵敏度高,与生物反应膜的连接更稳定,可重复性好,能够适应小型化、微型化、阵列化的设计需求,本发明还提供了该石墨烯生物传感器电极及其电极阵列的制备方法,可以实现批量化制备。(The invention relates to a graphene biosensor electrode which comprises an insulating base body, a first vertical graphene electrode, a first bonding pad and a first conductive hole, wherein the first conductive hole penetrates through the insulating base body, the first vertical graphene electrode and the first bonding pad are respectively positioned on two sides of the insulating base body, the first conductive hole is communicated with the first vertical graphene electrode and the first bonding pad up and down, and the insulating base body is a ceramic base. The invention further provides a preparation method of the graphene biosensor electrode and an electrode array thereof, and the preparation method can realize batch preparation.)

1. The utility model provides a graphite alkene biosensor electrode, includes insulating base member (1), its characterized in that still includes first upright graphite alkene electrode (21), first pad (41) and first electrically conductive hole (31), and first electrically conductive hole (31) run through insulating base member (1), first upright graphite alkene electrode (21) and first pad (41) are located respectively the both sides of insulating base member (1), first electrically conductive hole (31) communicate from top to bottom first upright graphite alkene electrode (21) and first pad (41), insulating base member (1) is the ceramic base.

2. The graphene biosensor electrode according to claim 1, wherein a first ceramic fence (51) is disposed on a peripheral side of the first upright graphene electrode (21);

a first biological reaction film layer (61) is arranged on the inner side of the first ceramic fence (51);

the first biological reaction film layer (61) is positioned on the peripheral side and the upper part of the first vertical graphene electrode (21), or the first biological reaction film layer (61) is only positioned on the upper part of the first vertical graphene electrode (21);

the first biological reaction film layer (61) is a functional material, a biological enzyme film or an ionic film.

3. The graphene biosensor electrode according to claim 2, wherein the three-dimensional surface of the first upright graphene electrode (21) is modified with one or a combination of two or more of gold, platinum, nickel, silver, titanium, ferrocene or prussian blue, and the modified material is in the form of nanoparticles; the graphene-based touch screen further comprises a second vertical graphene electrode (22), a second conductive hole (32) penetrating through the insulating base body (1), a second bonding pad (42) and a third bonding pad (43);

the edge of the second bonding pad (42) is provided with a transition angle smaller than 90 degrees, and the edge of the second bonding pad (42) and the insulating base body (1) form gentle transition connection; or the second bonding pad (42) is embedded into the upper surface of the insulating base body (1);

the second bonding pad (42) and the third bonding pad (43) are respectively positioned on two sides of the insulating base body (1), and the second conductive hole (32) is communicated with the second bonding pad (42) and the third bonding pad (43) up and down;

the second vertical graphene electrode (22) is located on the upper side of the second bonding pad (42), and the first vertical graphene electrode (21) and the second vertical graphene electrode (22) are located on the same side of the insulating base body (1).

4. The graphene biosensor electrode according to claim 3, wherein the first conductive hole (31), the second conductive hole (32) and the wire (7) are made of one or two of copper, gold, silver, platinum and tungsten;

the first conductive hole (31), the second conductive hole (32) and the lead (7) are prepared by electroplating, low-temperature sintering, high-temperature sintering or sputtering; the first bonding pad (41) and the third bonding pad (43) are electrically connected with a host system or an adapter in a physical contact mode, a soldering mode, a hot-press welding mode or an adhesion process.

5. The graphene biosensor electrode according to claim 1, wherein M holes are formed in the insulating substrate (1) to form an array of holes, the diameter of each hole is 0.05-0.2mm, the distance between every two holes is 0.3 ~ 3mm, each hole is filled with metal to form a first conductive hole (31), and a separate first upright graphene electrode (21) is formed on the surface of each first conductive hole (31);

each first vertical graphene electrode (21) is modified with different reaction film layers (61) and respectively prepared into a working electrode (601), a counter electrode (602) or a reference electrode (603), and the multi-electrode array can be used for realizing multi-dimensional biological signal detection;

unfilled vias (606) can be used to conduct gas; m is a natural number larger than 3, and the array is a rectangular array or a circular array.

6. The graphene biosensor electrode according to claim 1, wherein the first conductive via (3) is wall-divided into N or more non-uniform vertical partial via walls (311) insulated from each other in the axial direction; the first vertical graphene electrode (21) comprises N groups of vertical graphene clusters (211), and gaps are formed among the vertical graphene clusters (211) on the upper part of each vertical local pore wall (311); said first pad (41) being divided into N first pad subsections (411) insulated from each other;

each upright graphene cluster (211), the vertical local hole wall (311) and the first pad subsection (411) are communicated in sequence;

n is greater than or equal to 2 and is a natural number.

7. The graphene biosensor electrode according to claim 6, wherein the three-dimensional surface of the upright graphene cluster (211) is modified with gold nanoparticles, platinum nanoparticles, nickel nanoparticles, silver nanoparticles, titanium nanoparticles, ferrocene nanoparticles, or Prussian blue nanoparticles; different of the upright graphene clusters (211) modify nanoparticles of the same material or of different materials;

j layers of first ceramic fences (51) are arranged on the periphery side of the first upright graphene electrode (21), and J is an integer larger than or equal to 0;

a first biological reaction film layer (61) is arranged on the inner side of the first ceramic fence (51);

the first biological reaction film layer (61) is located on the periphery and the upper part of the vertical graphene cluster (211), or the first biological reaction film layer (61) is located only on the upper part of the vertical graphene cluster (211);

the individual upright graphene clusters (211) have different surface areas from one another.

8. A preparation process of a graphene biosensor electrode is characterized by comprising the following steps:

A. manufacturing a first conductive hole (31) and a first bonding pad (41) on an insulating base body (1) made of ceramic materials, wherein the first conductive hole (31) penetrates through the insulating base body (1) from top to bottom, and the first bonding pad (41) is positioned at the bottom of the first conductive hole (31);

B. polishing the upper part and the peripheral side of the first conductive hole (31) to be level with the surface of the substrate (1), wherein the surface roughness is not more than 0.8 mu m; or the smooth transition of the conductive hole (31) and the insulating base body (1) is realized through a control process;

C. manufacturing a first ceramic fence (51) on the peripheral side of the first conductive hole (31) by ceramic slurry;

D. preparing vertical graphene on the first conductive hole (31) to form a first vertical graphene electrode (21); the preparation method comprises local growth, or etching the unnecessary part with laser after the whole surface grows;

E. and arranging a first biological reaction film layer (61) on the three-dimensional surface of the first vertical graphene electrode (21) in the first ceramic fence (51).

9. The process for preparing the graphene biosensor electrode according to claim 8, wherein the step D is followed by the step E and further comprises:

D1. modifying one or more than two of gold nanoparticles, platinum nanoparticles, nickel nanoparticles, silver nanoparticles, titanium nanoparticles, ferrocene nanoparticles and Prussian blue nanoparticles on the surface of the first upright graphene electrode (21);

the A further comprises:

A1. manufacturing a second conductive hole (32), a second bonding pad (42) and a third bonding pad (43) on an insulating base body (1) made of ceramic materials, wherein the second conductive hole (32) penetrates through the insulating base body (1) from top to bottom, and the second bonding pad (42) and the third bonding pad (43) are respectively positioned at the upper part and the bottom of the second conductive hole (32);

the C further comprises:

C1. manufacturing a second ceramic fence (52) on the peripheral side of the second pad (42) by ceramic slurry;

the D further comprises:

D2. preparing vertical graphene on the upper part and the peripheral side of the second bonding pad (42) to form a second vertical graphene electrode (22);

the E further comprises:

E1. arranging a second biological reaction film layer (62) on the surface of the second vertical graphene electrode (22) in the second ceramic fence (52);

after E, the method further comprises the following steps:

F. sensor test calibration, and assembly applications.

10. The process for preparing the graphene biosensor electrode according to claim 8, wherein the steps of the A, B and C are alternately and cyclically performed as required.

Technical Field

The invention relates to the technical field of biochemical parameter acquisition, in particular to a graphene biosensor electrode and a preparation process thereof.

Background

Conventional biosensor electrodes are based on PET substrates, or paper-based disposable test strips, which are usually processed by screen printing. This test strip has several disadvantages:

① most adopt colorimetric method, can not be directly connected with electronic system, the detection result does not realize datamation, can not carry out subsequent statistical analysis, and has no more value, no possibility of data networking and big data analysis;

②, the disposable use means that there is no way to do systematic product-level testing and calibration, so the test strip's functional performance is good or bad, which cannot be determined completely in practice, and only statistical probability is needed, because the test strip needs to be destroyed once tested;

③, based on the printing process of PET and paper base, the consistency among individuals and the consistency among batches are difficult to guarantee, and the function of the test strip is a consumable material, which is also the reason that the results obtained by different hospitals, different devices and different test strips are difficult to be consistent;

④ the biosensor of test paper strip can only be made into plug-in structure due to the limitation of its own material and process characteristics, such as glass transition temperature, melting point, and poor binding force between substrate and slurry, and it can not be assembled with micro electronic system to make biosensor with better performance and experience, and there is no way to make further integration.

Due to the limitations of the process and material characteristics, the biosensor of the test strip has no way of achieving high sensitivity; there is no way to achieve miniaturization.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the graphene biosensor electrode provided by the invention is high in sensitivity and good in repeatability, and can meet the design requirement of miniaturization.

The utility model provides a graphite alkene biosensor electrode, includes insulating base member, first upright graphite alkene electrode, first pad and first electrically conductive hole, and first electrically conductive hole runs through insulating base member, and first upright graphite alkene electrode and first pad are located insulating base member's both sides respectively, and first electrically conductive hole communicates first upright graphite alkene electrode and first pad from top to bottom, and insulating base member is the ceramic base.

Preferably, a first ceramic fence is arranged on the periphery of the first upright graphene electrode;

a first biological reaction film layer is arranged on the inner side of the first ceramic fence;

the first biological reaction film layer is located on the periphery and the upper portion of the first vertical graphene electrode, or the first biological reaction film layer is located only on the upper portion of the first vertical graphene electrode.

Preferably, the first biological reaction membrane layer is a functional material, a biological enzyme membrane, an ionic membrane or the like.

Preferably, the three-dimensional surface of the first vertical graphene electrode is modified with

Gold nanoparticles, platinum nanoparticles, nickel nanoparticles, silver nanoparticles, titanium nanoparticles, ferrocene nanoparticles, or prussian blue nanoparticles; modifying nanoparticles of the same material or different materials by using different vertical graphene clusters;

methods of modification include physical vapor deposition of PCD, chemical vapor deposition of CVD, PECVD, or electroplating.

The periphery of the first vertical graphene electrode is provided with J layers of first ceramic fences, and J is an integer larger than or equal to 0.

Preferably, the graphene substrate further comprises a second vertical graphene electrode, a second conductive hole penetrating through the insulating substrate, a second pad and a third pad;

the second bonding pad and the third bonding pad are respectively positioned on two sides of the insulating base body, and the second conductive hole is communicated with the second bonding pad and the third bonding pad up and down;

the second vertical graphene electrode is located on the upper side of the second bonding pad, and the first vertical graphene electrode and the second vertical graphene electrode are located on the same side of the insulating base body.

Preferably, the edge of the second pad is provided with a transition angle smaller than 90 degrees, and the edge of the second pad and the insulating base body form a gentle transition connection; alternatively, the second pad is embedded in the upper surface of the insulating base 1.

Preferably, the first conductive hole, the second conductive hole and the wire are made of one or more of high-temperature resistant materials such as copper, gold, silver, platinum or tungsten; the first conductive hole, the second conductive hole and the lead are prepared by electroplating, low-temperature sintering, high-temperature sintering or sputtering and other processes; the first bonding pad and the third bonding pad are electrically connected with a host system or an adapter in a physical contact mode, a soldering mode, a hot-press welding mode, an adhesion mode and other processes.

Preferably, the first pad and the second pad form a pluggable electrical connection structure with the insulating base body.

Through a pluggable design, the graphene biosensor electrode can be provided with a standard interface and is connected with a standard test circuit, and manual intervention and manual judgment are not needed during use; the use is convenient, and the deviation caused by artificial judgment can be avoided.

The first bonding pad and the second bonding pad extend to the edge of the insulating base body; or the first bonding pad and the second bonding pad extend to the edge of the insulating base body through the metal wire; or one of the first pad and the second pad extends to the edge of the insulating base body, and the other pad is positioned at the edge of the insulating base body.

Preferably, M holes are prepared on an insulating substrate to form an array, the diameter of each hole is 0.05-0.2mm, the distance between every two holes is 0.3 ~ 3mm, each hole is filled with metal to form a first conductive hole, and an independent first vertical graphene electrode is prepared on the surface of each first conductive hole;

each first vertical graphene electrode modifies different reaction film layers and is respectively prepared into a working electrode and a counter electrode (or a reference electrode), and the multi-electrode array can be used for realizing multi-dimensional biological signal detection;

unfilled vias can be used to conduct gas; m is a natural number larger than 3, and the array is a rectangular array or a circular array.

Preferably, the first conductive hole is divided into more than N uneven vertical partial hole walls which are insulated from each other along the axial direction; the first vertical graphene electrode comprises N groups of vertical graphene clusters, and a gap is formed between the vertical graphene clusters on the upper part of each vertical local hole wall; the first pad is divided into N first pad subsections which are insulated from each other;

each vertical graphene cluster, the vertical local hole wall and the first pad subsection are communicated in sequence;

n is greater than or equal to 2 and is a natural number.

Preferably, the upper surface and the peripheral side of the vertical graphene cluster are modified with nanogold, nano platinum or nano nickel;

a first ceramic fence is arranged on the periphery of the first vertical graphene electrode;

a first biological reaction film layer is arranged on the inner side of the first ceramic fence;

the first biological reaction film layer is positioned on the peripheral side and the upper part of the vertical graphene cluster, or the first biological reaction film layer is only positioned on the peripheral side of the vertical graphene cluster;

each different upright graphene cluster has a different surface area from the other.

The walls of the hole are represented by the intersecting circles.

A preparation process of a graphene biosensor electrode comprises the following steps:

A. manufacturing a first conductive hole and a first bonding pad on an insulating base body made of ceramic materials, wherein the first conductive hole vertically penetrates through the insulating base body, and the first bonding pad is positioned at the bottom of the first conductive hole;

B. polishing the upper part and the peripheral side of the first conductive hole to be level with the surface of the substrate, wherein the surface roughness is not more than 0 μm; or the smooth transition of the conductive hole and the insulating matrix is realized by controlling the process;

C. manufacturing a first ceramic fence by ceramic slurry on the peripheral side of the first conductive hole;

D. preparing vertical graphene on the first conductive hole to form a first vertical graphene electrode; the preparation method comprises local growth, or laser etching the unnecessary part after the whole surface grows;

E. in the first ceramic fence, a first biological reaction film layer is arranged on the three-dimensional surface of the first vertical graphene electrode.

Preferably, D is followed by E and further comprises:

D1. modifying nanoparticles such as gold nanoparticles, platinum nanoparticles, nickel nanoparticles, silver nanoparticles, titanium nanoparticles, ferrocene nanoparticles and Prussian blue nanoparticles on the surface of the first vertical graphene electrode.

Preferably, a further comprises:

A1. manufacturing a second conductive hole, a second bonding pad and a third bonding pad on an insulating base body made of ceramic materials, wherein the second conductive hole penetrates through the insulating base body from top to bottom, and the second bonding pad and the third bonding pad are respectively positioned at the upper part and the bottom of the second conductive hole;

c also includes:

C1. manufacturing a second ceramic fence by ceramic slurry on the peripheral side of the second bonding pad;

d, also comprising:

D2. preparing vertical graphene on the upper part and the peripheral side of the second bonding pad to form a second vertical graphene electrode;

e, further comprising:

E1. and in the second ceramic fence, a second biological reaction film layer is arranged on the surface of the second vertical graphene electrode.

After E, the method further comprises the following steps:

F. sensor test calibration, and assembly applications.

Preferably, a further comprises:

A2. vertically cutting the first conductive hole to enable the wall body of the first conductive hole to be divided into more than N uneven vertical partial hole walls which are insulated with each other along the axial direction;

dividing the first vertical graphene electrode into N groups of vertical graphene clusters, wherein a gap is formed between the vertical graphene clusters on the upper part of each vertical local hole wall;

dividing the first pad into N first pad subsections which are insulated from each other;

each vertical graphene cluster, the vertical local hole wall and the first pad subsection are communicated in sequence;

n is greater than or equal to 2 and is a natural number.

The invention has the beneficial effects that: the utility model provides a graphite alkene biosensor electrode, includes insulating base member, first upright graphite alkene electrode, first pad and first electrically conductive hole, and first electrically conductive hole runs through insulating base member, and first upright graphite alkene electrode and first pad are located insulating base member's both sides respectively, and first electrically conductive hole communicates first upright graphite alkene electrode and first pad from top to bottom, and insulating base member is the ceramic base. The insulating substrate is arranged to be a ceramic substrate, the requirement of repeated use can be met, the vertical graphene electrode is arranged, the surface area of the vertical graphene electrode is large, the sensitivity to electricity is high, the repeatability is good, and the design requirement of miniaturization can be met.

Drawings

The graphene biosensor electrode according to the present invention will be further described with reference to the accompanying drawings.

Fig. 1 is a cross-sectional view of one embodiment of a graphene biosensor electrode of the present invention.

Fig. 2 is a cross-sectional view of another embodiment of a graphene biosensor electrode according to the present invention.

Fig. 3 is a cross-sectional view of yet another embodiment of a graphene biosensor electrode of the present invention.

Fig. 4 is a cross-sectional view of an intelligent biosensor embodiment of a graphene biosensor electrode according to the present invention.

Fig. 5 is a front view of a graphene biosensor electrode of the present invention.

Fig. 6 is a view of the reverse side of a graphene biosensor electrode of the present invention.

Fig. 7 is a front view of an application of a vertical graphene biosensor array according to the present invention.

Fig. 8 is a front view of another example of an application of a vertical graphene biosensor array according to the present invention.

Fig. 9 is a cross-sectional view of another example of an application of a vertical graphene biosensor array according to the present invention.

In the figure:

1-an insulating matrix; 21-a first upright graphene electrode; 22-a second vertical graphene electrode; 211-upright graphene clusters; 31-a first conductive via; 311-vertical partial hole walls; 32-a second conductive via; 41-a first pad; 411-first pad subsection; 42-a second pad; 43-a third pad; 51-a first ceramic fence; 52-a second ceramic fence; 61-a first bioreaction membrane layer; 62-a second bioreaction membrane layer; 601-a working electrode; 602-a counter electrode; 603-a reference electrode; 606-a through hole; 7-a metal wire; 81-nanogold; 82-nano nickel; 8-a connecting material; 9-a circuit chip; 10-a biosensor; 101-a carrier plate; 102-a connecting member; 103-host system.

Detailed Description

The graphene biosensor electrode according to the present invention is further described with reference to fig. 1 ~ 9.