Surface chemical treatment apparatus for drawing predetermined pattern by carrying out a chemical treatment
09839932 · 2017-12-12
Assignee
- Shimadzu Corporation (Kyoto, JP)
- Tokyo Metropolitan University (Tokyo, JP)
- Waseda University (Tokyo, JP)
Inventors
- Katsumi Uchiyama (Tokyo, JP)
- Hizuru Nakajima (Tokyo, JP)
- Ming Yang (Tokyo, JP)
- Hulie Zeng (Tokyo, JP)
- Yoshiyuki Sugahara (Tokyo, JP)
- Takahiro Nishimoto (Kyoto, JP)
Cpc classification
B05B7/06
PERFORMING OPERATIONS; TRANSPORTING
B05B7/14
PERFORMING OPERATIONS; TRANSPORTING
B05B14/10
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
C23F1/08
CHEMISTRY; METALLURGY
B05C5/02
PERFORMING OPERATIONS; TRANSPORTING
C03C15/00
CHEMISTRY; METALLURGY
B05C3/20
PERFORMING OPERATIONS; TRANSPORTING
International classification
C23F1/08
CHEMISTRY; METALLURGY
B05C3/20
PERFORMING OPERATIONS; TRANSPORTING
B05B7/06
PERFORMING OPERATIONS; TRANSPORTING
B05C9/06
PERFORMING OPERATIONS; TRANSPORTING
B05B7/14
PERFORMING OPERATIONS; TRANSPORTING
B05C5/02
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A surface chemical treatment apparatus provided with: a first conduit having an opening at one end and communicating with a liquid supply means at the other end; a second conduit having at one end an opening that surrounds the opening of the first conduit and communicating with a liquid suction means at the other end; and a moving mechanism for moving the openings of the first and second conduits relative to the solid phase surface, so as to make a surface chemical treatment possible in a fine pattern by allowing the patterning solution to be dispensed through the opening of the first conduit while allowing the solution to be suctioned up together with the surrounding liquid phase or gas phase medium through the opening of the second conduit that surrounds the opening of the first conduit and, thus, preventing seepage of the solution in all directions.
Claims
1. A surface chemical treatment apparatus for drawing a predetermined pattern by carrying out a chemical treatment in the predetermined pattern through drawing on a solid phase surface placed in a liquid phase medium, comprising: a container including the liquid phase medium, the solid phase surface being provided within the liquid phase medium; a first conduit having an opening at one end and communicating at the other end with a liquid supply section for supplying a patterning solution that draws the predetermined pattern on the solid phase surface by reacting with the solid phase surface for the chemical treatment on the surface; a conduit for supplying a sheath liquid through which the sheath liquid is supplied into said first conduit so that a sheath flow can be created within the first conduit so as to converge the patterning solution to a center of the first conduit; and a second conduit having at one end an opening that surrounds the opening of said first conduit and communicating with a liquid suction section at the other end; wherein a moving mechanism for moving the container so that the solid phase surface is moved relative to the openings of the first and second conduits while the solid phase surface is immersed within the liquid phase medium, a chemically treated region of the predetermined pattern is created by moving the openings of the first and second conduits relative to the solid phase surface while allowing said patterning solution to be supplied into said first conduit from said liquid supply section, and at the same time, allowing said sheath liquid to be supplied into said first conduit from said conduit for supplying the sheath liquid so that said patterning solution is converged to the center of the first conduit, and the patterning solution is then dispensed through the opening of the first conduit, and while driving the liquid suction section so that the patterning solution dispensed through the opening of the first conduit is suctioned up together with the liquid phase medium through the opening of the second conduit.
2. The surface chemical treatment apparatus according to claim 1, wherein said moving mechanism is a mechanism for moving the openings and the solid phase surface in a three-dimensional manner relative to each other, and the openings and the solid phase surface move relative to each other according to a route that has been set in advance by a setting unit.
3. The surface chemical treatment apparatus according to claim 1, wherein said first and second conduits, or said first and second conduits together with the conduit for supplying sheath liquid, are made of a structure formed of silicon.
4. The surface chemical treatment apparatus according to claim 1, wherein the moving mechanism is provided outside of the container and under the solid phase surface.
5. A surface chemical treatment apparatus, comprising: a container that contains a liquid phase medium in which a solid phase surface on which a patterning process is to be carried out is immersed; a stage on which said container is placed; a moving mechanism for moving said stage; a dual conduit made up of a first conduit having a first opening at the bottom end and a second conduit which is arranged so as to surround said first conduit and which has a second opening that surrounds said first opening; a pipe which communicates with the upper end of said first conduit and through which a patterning solution is supplied via a pump for injection; a conduit for supplying a sheath liquid which is connected to an opening for sheath formation provided in proximity to the upper end of said first conduit and through which the sheath liquid is supplied via a pump for supplying the sheath liquid; and a pipe that communicates with the upper end of said second conduit and is connected to a pump for discharge that suctions a liquid, wherein said first opening and said second opening are arranged so as to face the solid phase surface within said liquid phase medium, and a pattern is drawn on the solid phase surface through a chemical treatment by moving said stage while allowing the patterning solution to be dispensed through the first opening, and at the same time, allowing the patterning solution to be suctioned up together with the liquid phase medium through the second opening.
6. The surface chemical treatment apparatus according to claim 5, wherein the moving mechanism is provided outside of the container and under the solid phase surface.
7. The surface chemical treatment apparatus according to claim 5, wherein said moving mechanism is a mechanism for moving the openings and the solid phase surface in a three-dimensional manner relative to each other, and the openings and the solid phase surface move relative to each other according to a route that has been set in advance by a setting unit.
8. The surface chemical treatment apparatus according to claim 5, wherein said first and second conduits, or said first and second conduits together with the conduit for supplying sheath liquid, are made of a structure formed of silicon.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
DETAILED DESCRIPTION OF EMBODIMENTS
(3) In the following preferred embodiments according to the present invention are described in reference to the drawings.
(4) A solid phase surface 1 such as of a glass material or a silicon substrate on which a patterning process is to be carried out is supported by a support member (not shown) so as to be placed within a container 3 in which a gas or liquid phase medium, liquid phase medium 2 in this example, is held and, thus, is subject to a treatment in a state of immersion within the liquid phase medium 2. The container 3 is fixed onto a stage 4. The stage 4 is driven by a moving mechanism 21 so as to move in the x and y directions along the solid phase surface 1 as well as in the z direction that is orthogonal thereto. The moving mechanism 21 is subject to control by a control unit 22 and the control unit 22 controls the moving mechanism 21 so that the stage 4 moves through the movement route set by a setting unit 23 and stored in a memory unit 24. Here, the control unit 22, the setting unit 23 and the memory unit 24 can be formed of a computer and its peripheral equipment.
(5) A dual conduit made up of a first conduit 11 and a second conduit 12 that is provided so as to surround the first conduit 11 is provided above the stage 4. One end (bottom end) of each of these conduits 11 and 12 forms an opening 11a and 12a, respectively, and these openings 11a and 12a face the solid phase surface 1 in a state of immersion within the liquid phase medium 2.
(6) The other end (upper end) 11b of the first conduit 11 communicates with the opening for dispensing 14a of a pump for injection 14 via a pipe 13. The opening for suction 14b of this pump for injection 14 is connected to a patterning solution tank (not shown) for storing a patterning solution 31. The patterning solution 31 is provided by dissolving a solute 32 into a solvent 33, and the solvent 33 may be the same liquid as the liquid phase medium 2 in the container 3.
(7) The other end (upper end) 12b of the second conduit 12 communicates with the opening for suction 16a of a pump for discharge 16 via a pipe 15. The opening for dispensing 16b of this pump for discharge 16 communicates with an opening for liquid discharge (not shown).
(8) How the above-described embodiment operates is described below. Prior to the actual driving of the apparatus, a moving route of the stage 4 is set in advance through the operation of the setting unit 23 on the basis of a pattern to be drawn on the solid phase surface 1. The contents of this setting are stored in the memory unit 24.
(9) When a drive start instruction is given to the apparatus both the pump for injection 14 and the pump for discharge 16 are driven while the moving mechanism 21 is controlled and driven along the route of movement stored in the memory unit 24 so as to move the stage 4. The pump for injection 14 is driven so that the patterning solution 31 flows into the first conduit 11 and, then, flows out of the conduit towards the solid phase surface 1 through the opening 11a at the lower end of the conduit. When the patterning solution 31 flows out, the solute 32 that has been dissolved into the solvent 33 is fixed in a predetermined pattern on the solid phase surface 1 and, thus, a patterning region 34 is created by the solute 32. At this time, the pump for discharge 16 is also driven and, therefore, the solvent 33 in the patterning solution 31 that has flown out through the opening 11a of the first conduit 11 and part of the solute 32 are suctioned up through the opening 12a of the second conduit 12 that is located so as to surround the opening 11a as shown by the arrow A in the figure and, at the same time, the surrounding liquid phase medium 2 is also suctioned up through the opening 12a of the conduit 12 as shown by the arrow B.
(10) During this operation the patterning solution 31 that has been dispensed through the opening 11a of the first conduit 11 is suctioned up through the opening 12a of the second conduit 12 that is positioned so as to surround the opening 11a and, therefore, the spread of the patterning region 34 where the solute 32 is fixed through contact with the solid phase surface 1 can be suppressed in all directions on the solid phase surface 1 and, thus, seepage can be prevented. As a result, the solute 32 can be condensed and fixed in a microscopic region and, thus, the fixation efficiency increases.
(11) An example of a microreactor that is fabricated in accordance with the above-described embodiment is described below. This example shows a structure wherein a pattern is drawn with a temperature responsive high polymer on only a target surface of a capillary plate made of glass. The microreactor allows a substance A to be fixed to the capillary portion of this capillary plate so that a substance B reacts on the temperature responsive high polymer side. The reactor makes it possible for the substances A and B to react with each other only in a specified portion through hydrophilic control (Laplace pressure control) using a temperature responsive high polymer.
(12) In the structure wherein a pattern is drawn with a temperature responsive high polymer on the target surface of a capillary plate, permeability control by means of temperature can be carried out in a position selective manner. That is to say, at a temperature higher than the transition point the surface becomes hydrophobic and, thus, becomes impermeable. At a temperature lower than the transition point the surface becomes hydrophilic and, thus, becomes permeable. In summary, in the case wherein water is used as the solvent, the Laplace pressure is controllable, which makes it possible to operate the microreactor as a microreactor having a switching function.
(13) In order to fabricate a microreactor as described above, first, a bromo group is introduced onto the surface of a capillary plate (using isopropylamide or the like) and this capillary plate is immersed in a mixture of methanol and DMF (in a ratio of 1:1) that contains 1% to 5% of N,N,N′,N″,N″-pentamethyldiethylenetriamine and 0.1% to 5% of copper bromide (I) (hereinafter referred to as solvent 1).
(14) Next, the above-described embodiment of the present invention is set so that a solution that is gained by diluting 0.1% to 5% of N-isopropylacrylamide with the above-described solution 1 (hereinafter referred to as reagent 1) is supplied to the first conduit 11, and the opening 11a of the first conduit 11 is located in close proximity to the target point on the surface of the capillary plate. The reagent 1 is dispensed through the opening 11a of the first conduit 11 at a rate of 1 μL to 100 μL per minute, and the solvent 1 and the reagent 1 are suctioned up through the opening 12a of the second conduit 12 at a rate of 1 μL to 500 μL per minute and, thus, the target point and vicinity are chemically modified. The capillary plate and the first and second conduits 11 and 12 can be moved relative to each other in the x and y directions by driving the stage 4 so that a pattern can be drawn in a specified region. This is implemented in a nitrogen atmosphere.
(15) As a result, a temperature responsive high polymer can be introduced only onto the target surface of a capillary plate.
(16) Next, another embodiment of the present invention is described.
(17) The embodiment in
(18) This structure utilizing a sheath flow makes it possible to further miniaturize the patterning as compared to the above example. In particular, even when there is a restriction on the diameter of the opening 11a of the first conduit 11 due to manufacturing technology or ease of maintenance, it is possible to draw lines that are narrower than the diameter of the opening 11a.
(19) Though glass pipes and resin pipes are used for the first conduit 11, the second conduit 12, the conduit for supplying a sheath liquid 52 and the like in the above-described embodiments for illustrative purposes, the present invention is not limited to these cases and, in addition to the usage of pipes of these materials, pipes may be formed of a structure made of Si in accordance with MEMS technology having a structure equivalent to the above-described pipes and, in such cases, further miniaturization of the patterning may be possible.
(20) Though the above-described embodiments provide examples wherein the solid phase surface is patterned while the stage on which the solid phase surface is mounted is being moved, the present invention can, of course, adopt a structure having a mechanism wherein the solid phase surface is fixed and the first and second conduits are moved.
INDUSTRIAL APPLICABILITY
(21) According to the present invention, target molecules can be formed in any pattern in any location on a glass material or on a silicon substrate, for example, and, thus, the present invention can be effectively applied to an apparatus that carries out fine pattern surface chemical treatment on a solid phase surface using a solution, such as fabrication of various types of fine sensors or sensor arrays, or patterning of molecules having a thionyl group on a metal film, or patterning of other molecules in specific portions on top of the patterned molecules having a thionyl group.
EXPLANATION OF SYMBOLS
(22) 1 solid phase
(23) 2 liquid phase (or gas phase)
(24) 3 container
(25) 4 stage
(26) 11 first conduit
(27) 12 second conduit
(28) 13 pipe
(29) 14 pump for injection
(30) 15 pipe
(31) 16 pump for discharge
(32) 21 moving mechanism
(33) 22 control unit
(34) 23 setting unit
(35) 24 memory unit
(36) 31 patterning solution
(37) 32 solute
(38) 33 solvent
(39) 34 patterning region
(40) 35 sheath liquid
(41) 51 opening for sheath formation
(42) 52 conduit for supplying sheath liquid
(43) 53 pump for supplying sheath liquid