JP2010054451A - Micro analysis device, manufacturing method therefor, and manufacturing apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology for bonding various substrates by using a specifically treated photosensitive polyimide resin. <P>SOLUTION: The method of manufacturing a micro analysis device includes a step of forming a photosensitive polyimide precursor layer on a first substrate 12; a pattern formation step of forming a pattern of the photosensitive polyimide precursor layer; a first heating step of forming a photosensitive polyimide resin layer 17 by heating the patterned photosensitive polyimide precursor layer to 200°C to 350°C under an environment of 50 ppm or less of oxygen concentration; a step of sandwiching the photosensitive polyimide resin layer 17 between a second substrate 14 and the first substrate 12; and a second heating step of heating the first substrate 12 and the second substrate 14 at the same temperature as the highest temperature in the first heating step or at a temperature within 30°C from and lower than the highest temperature in the first heating step while pressing at 16.3 MPa to 49 MPa. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a microanalyzer, a manufacturing method thereof, and a manufacturing apparatus thereof.

  2. Description of the Related Art Conventionally, a method has been disclosed in which a resin material is sandwiched between a plurality of opposing substrates and each substrate is joined by pressurization (for example, Patent Document 1 or Patent Document 2). However, in the prior art, as a specific embodiment, a voltage of several tens of volts to 200 volts is always applied between two substrates sandwiching the resin. In the case of the bonding technique described in Patent Document 2 below, the heating temperature at the time of bonding the substrates after the resin material is sandwiched between the plurality of substrates is set higher than the heating temperature of the resin material. Has been. In such a temperature setting, it is extremely difficult or impossible to completely release the gas caused by the volatile substance by the first heat treatment. Therefore, one of the important technical issues to be noticed when bonding using resin is the problem of the gas released from the resin during the bonding process, in other words, the problem of the quality of the bonded substrate. The present situation is that no solution is presented.

On the other hand, in recent years, especially in the chemical field, the analysis system has been miniaturized and integrated using elemental technology in the field of MEMS (Micro Electro Mechanical Systems), and so on, which is referred to as a micro chemical analysis system (MicroTAS) 1 Two microanalyzers are actively researched and developed. A feature of this microanalyzer is that rapid analysis is possible with a very small amount of sample, but in order to make the analysis accurate, impurities are introduced from members constituting the sample introduction part, flow path, etc. Should be avoided. Therefore, particularly in the manufacturing process of the microanalyzer, the above-described substrate bonding technique or bonding technique occupies an important position.
JP 2004-268323 A JP 2005-7734 A

  As described above, conventionally, in order to realize a sufficient bonding strength by bonding a plurality of substrates using a resin, bonding at a temperature exceeding the temperature at the time of applying a voltage to the resin or heating the resin is performed. The heat treatment of time was necessary. Therefore, in the prior art, instead of obtaining sufficient joint strength, the cost of equipment increases due to the addition of equipment for supplying voltage, and the final device due to the gas released from the resin that is inevitably generated The problem of a decrease in reliability occurs.

  The present invention proposes a microanalyzer that uses a resin as a part of the inner wall of a flow path by solving such a technical problem. The inventors have already applied Japanese Patent Application No. 2008-41623 for a substrate bonding technique that satisfies both of the two technical problems of significant reduction of released gas due to volatile substances in polyimide resin and acquisition of high bonding strength. Proposed in After that, the inventors conducted extensive research focusing on the high thermal stability, physical and chemical stability of polyimide resin, and as a result, microanalyzed the bonding technology for substrates using the aforementioned polyimide resin. It has been found that, by applying to the manufacture of the device, the manufacturing cost can be reduced while ensuring high reliability.

  One method for manufacturing a microanalyzer according to the present invention includes a step of forming a photosensitive polyimide precursor layer on a first substrate, a pattern forming step of forming a pattern of the photosensitive polyimide precursor layer, and an oxygen concentration. After the first heating step of forming the photosensitive polyimide resin layer by heating the photosensitive polyimide precursor layer on which the pattern is formed at 200 ° C. or higher and 350 ° C. or lower in an environment of 50 ppm or less, the second substrate And sandwiching the photosensitive polyimide resin layer between the first substrate and the first substrate, and pressing the first substrate and the second substrate at 16.3 MPa to 49 MPa, A second heating step of heating at a temperature lower than the maximum temperature of the first heating step within a difference between the same temperature as the highest temperature or the highest temperature of the first heating step within 30 ° C.

  According to the method for manufacturing the microanalyzer, the first substrate and the second substrate are bonded by sandwiching the patterned photosensitive polyimide as an adhesive layer, and the photosensitive polyimide resin is attached to the inner wall of the flow path. Therefore, the manufacturing process of the microanalyzer can be simplified and the manufacturing cost can be reduced. In other words, as in the prior art, after removing a part of the surface of the first substrate or the second substrate by a complicated etching technique, the first substrate and the second substrate are bonded together by another joining means. I don't need it. In addition, since the photosensitive polyimide precursor layer is heat-treated in an environment in which the oxygen concentration is controlled, the detailed reason is not yet clear, but the photosensitive polyimide resin obtained by the heating is unique for bonding substrates. It has special properties. As a result, even if the heating temperature after the first substrate and the second substrate are bonded is the same as or slightly lower than the maximum temperature during the modification of the photosensitive polyimide resin, it can withstand practical use. Not only can the substrate bonding strength be obtained, but also the amount of gas released from the resin after bonding is significantly reduced. Therefore, the reliability of the microanalyzer manufactured by the above manufacturing method is increased.

  Further, in one microanalyzer of the present invention, the first substrate and the second substrate are joined by sandwiching the patterned photosensitive polyimide resin layer as an adhesive layer, the first substrate, the second substrate, and The photosensitive polyimide resin layer forms a tubular flow path.

  According to this microanalyzer, the first substrate and the second substrate are bonded by sandwiching the patterned photosensitive polyimide resin layer as an adhesive layer, and the photosensitive polyimide resin is part of the inner wall of the flow path. Therefore, the manufacturing process of the microanalyzer can be simplified and the manufacturing cost can be reduced. In addition, since the material other than the substrate is only a polyimide resin having high thermal stability and chemical stability, this microanalyzer can easily improve the heat resistance and stability of the entire apparatus.

  Moreover, the manufacturing apparatus of one microanalyzer according to the present invention includes a pattern formation processing unit that forms a pattern of the photosensitive polyimide precursor layer on the first substrate, and the pattern in an environment where the oxygen concentration is 50 ppm or less. A first heat treatment section for forming the photosensitive polyimide resin layer by heating the formed photosensitive polyimide precursor layer at 200 ° C. or higher and 350 ° C. or lower, and the first heat treatment section sandwiching the photosensitive polyimide resin layer therebetween. A bonding portion for bonding the substrate and the second substrate, and the same temperature as the maximum processing temperature of the first heat treatment unit, while pressing the first substrate and the second substrate at 16.3 MPa or more and 49 MPa or less, Or the 2nd heat processing part heated at the temperature lower than the maximum processing temperature of the 1st heat processing part whose difference with the maximum processing temperature of the 1st heat processing part is less than 30 degreeC is provided.

According to this microanalyzer manufacturing apparatus, first, the photosensitive polyimide resin layer is heat-treated in an environment in which the oxygen concentration is controlled in the first heat treatment unit, but the detailed reason is not yet clear, Photosensitive polyimide resin has unique properties suitable for bonding substrates. As a result, the heating temperature in the second heat treatment unit after the first substrate and the second substrate are bonded in the bonding unit is the same as or higher than the maximum temperature during the modification of the photosensitive polyimide resin described above. Even if the temperature is slightly low, not only the substrate bonding strength that can withstand practical use is obtained, but also the amount of gas released from the resin after bonding is significantly reduced. Therefore, the microanalyzer manufacturing apparatus can simplify the manufacturing process of the microanalyzer and reduce the manufacturing cost, and can manufacture a highly reliable microanalyzer.

  In addition, “pressurization” in each of the above-described inventions means that pressure is applied in a direction in which a plurality of substrates are bonded.

  Furthermore, in the manufacturing method of one regenerative microanalyzer according to the present invention, the alkali-resistant first substrate and the alkali-resistant second substrate are joined by sandwiching the photosensitive polyimide resin layer on which the pattern is formed as an adhesive layer. After the fluid has flowed at least once through the tubular flow path formed by the first substrate, the second substrate, and the photosensitive polyimide resin layer of the microanalyzer, the microanalyzer described above is placed in an alkaline solution. A step of immersing in

  According to this method of manufacturing a reproducible microanalyzer, since the material other than the alkali-resistant substrate constituting the microanalyzer is only a polyimide resin having high chemical stability, a fluid (typically Even if it is a microanalyzer in which a liquid has flowed, a microanalyzer that can be reused can be manufactured by immersing it in an alkali solution. However, the type of the alkali solution is not particularly limited in the present invention. Typically, an aqueous sodium hydroxide (NaOH) solution, an aqueous potassium hydroxide (KOH) solution, or sodium hypochlorite can be given. Similarly, in the present invention, the type of alkali-resistant substrate is not particularly limited, but typically, quartz (natural or synthetic) and aluminosilicate glass can be mentioned.

  According to one method for manufacturing a microanalyzer of the present invention, the first substrate and the second substrate are bonded by sandwiching the patterned photosensitive polyimide as an adhesive layer, and the photosensitive polyimide resin is flowed. Therefore, the manufacturing process of the microanalyzer can be simplified and the manufacturing cost can be reduced. Further, according to this manufacturing method, not only the substrate bonding strength that can withstand practical use can be obtained, but also the amount of gas released from the resin after bonding can be significantly reduced, so that the reliability of the manufactured microanalyzer can be improved. Rise.

  Further, according to one microanalyzer of the present invention, the first substrate and the second substrate are bonded by sandwiching the patterned photosensitive polyimide as an adhesive layer, and the photosensitive polyimide resin is used for the flow path. Since it can be used as a part of the inner wall, the manufacturing process of the microanalyzer can be simplified and the manufacturing cost can be reduced. In addition, since the material other than the substrate is only a polyimide resin having high thermal stability and chemical stability, this microanalyzer can easily improve the heat resistance and stability of the entire apparatus.

  In addition, according to the apparatus for manufacturing a microanalyzer of the present invention, the manufacturing process of the microanalyzer can be simplified and the manufacturing cost can be reduced, and a highly reliable microanalyzer can be manufactured. it can.

  Moreover, according to the manufacturing method of one regenerative microanalyzer of the present invention, a microanalyzer that can be used again can be manufactured by immersing it in an alkaline solution even if it is once used.

  Next, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In this description, common parts are denoted by common reference symbols throughout the drawings unless otherwise specified. In the drawings, the elements of the present embodiment are not necessarily shown to scale. Moreover, in order to make each drawing easy to see, some constituent members or symbols may be omitted.

<First Embodiment>
FIG. 1 is a plan view of one microanalyzer manufacturing apparatus 100 according to this embodiment, and FIGS. 2 and 3 are heating and pressurizing parts of the microanalyzer manufacturing apparatus 100 shown in FIG. 4 is a cross-sectional view of the chamber 20 during different heat treatment purposes. FIG. FIG. 4 is a plan view of the microanalyzer 10 according to one embodiment of the present invention, and FIG. 5 is an enlarged view of a part (Z portion) of FIG. 6A to 6D are schematic diagrams for explaining the manufacturing process flow of the microanalyzer 10 of this embodiment, and FIG. 7 is a diagram showing the conditions of the manufacturing process of the microanalyzer 10 of this embodiment. is there.

  The microanalyzer manufacturing apparatus 100 in the present embodiment shown in FIG. 1 is a multi-chamber processing apparatus. Specifically, the micro-analyzer manufacturing apparatus 100 includes a load lock chamber 40, a transfer chamber 50, a heating / pressurizing chamber 20 that heats and / or pressurizes a substrate, and a plurality of substrates attached with high accuracy. And an alignment chamber 30 to be combined. The micro-analyzer manufacturing apparatus 100 according to the present embodiment further includes a pattern formation processing unit 60 that forms a pattern of the photosensitive polyimide precursor layer on the substrate. Here, the pattern formation processing unit 60 may be applied with pattern formation using a known photolithography technique or pattern formation using a known ink jet technique.

  The load lock chamber 40 and the transfer chamber 50 are provided with a known substrate transfer mechanism. The load lock chamber 40 is a place for taking in and out the substrate before and after processing, and the transfer chamber 50 plays a role of transferring the substrate to a plurality of processing chambers or the load lock chamber 40. Further, the load lock chamber 40, the transfer chamber 50, and the alignment chamber 30 can be exhausted by a pump (not shown).

  Here, as shown in FIG. 2 or FIG. 3, the heating and pressurizing chamber 20 includes the stage 22 on which the substrate is placed, the pressing plate 23, and the temperature of the heater embedded in the stage 22 and the pressing plate 23. Heater control units 24 and 25 for controlling are provided. The stage 22 and the pressing plate 23 also serve as a pressing plate when the substrate is pressed. The heating and pressurizing chamber 20 is connected to a pump 26 for depressurizing the inside of the chamber 21 and to a nitrogen gas cylinder 27 that supplies nitrogen gas into the chamber 21.

  Although not shown, the heater control units 24 and 25 receive signals from thermocouples provided on a part of the stage 22 and the pressing plate 23 by a known control method and receive the signals from the stage 22 and the pressing plate 23. Control the temperature. Further, since at least one of the stage 22 and the pressing plate 23 can be moved up and down by a known lifting mechanism (not shown), the substrate placed on the stage 22 can be pressed. In addition, the pressure value applied to the substrate is controlled by control means using a commercially available pressure sensor (for example, a sensor (model number: VLC-50KNH229) manufactured by Valcom Co., Ltd.). The amount of nitrogen gas supplied from the nitrogen gas cylinder 27 is accurately controlled by a known valve 28 and a controller (not shown) that controls them.

  Next, the microanalyzer 10 will be described. The microanalyzer 10 of the present embodiment is formed by bonding a first substrate 12 that is one substrate and a second substrate 14 that is the other substrate, using a photosensitive polyimide resin layer 17 as an adhesive layer. . Here, the material of the first substrate 12 is silicon, and the material of the second substrate 14 is Pyrex (registered trademark) glass. The microanalyzer 10 of the present embodiment is configured such that one or a plurality of specimens or reagents are introduced from the injection opening 19 a and are taken out from the discharge opening 19 b via the tubular channel 18. . The trade name of the photosensitive polyimide resin (photosensitive polyimide precursor) used in this embodiment is DURIMIDE (registered trademark) 7510.

  4 and 5 show the arrangement of the patterned photosensitive polyimide resin layer 17 that is visually recognized by arranging the second substrate 14 in the microanalyzer 10 on the upper side. In order to make the drawing easy to see, the photosensitive polyimide resin layer 17 is colorless, and only the boundary line between the photosensitive polyimide resin layer 17 and the tubular flow path 18 is shown.

  In the present embodiment, the photosensitive polyimide resin layer 17 forms a part of the inner wall of the tubular flow path 18 in the microanalyzer 10. Specifically, the tubular flow path 18 is formed by a silicon substrate that is the first substrate 12, a Pyrex (registered trademark) glass substrate that is the second substrate 14, and the photosensitive polyimide resin layer 17. Therefore, the microanalyzer 10 of this embodiment has high heat resistance. For example, the microanalyzer 10 of the present embodiment obtains a highly reliable and reproducible analysis result because the degradation of the tubular flow path 18 hardly deteriorates even during analysis in an environment of about 100 ° C. be able to.

  In addition, regarding the microanalyzer 10 of this embodiment, in addition to the silicon substrate and the Pyrex (registered trademark) glass substrate, which are alkali-resistant substrates, only the chemically stable photosensitive polyimide resin layer 17 has a tubular flow path. It constitutes the inner wall. Therefore, the microanalyzer 10 of the present embodiment is a microanalyzer that can be used again by immersing it in an alkaline solution even after it has been used once. In this embodiment, the microanalyzer 10 once used was immersed in an aqueous sodium hypochlorite solution for 10 minutes and then rinsed with physiological saline. After that, when the microanalyzer 10 was used again for the same analysis as the first time, a result equivalent to the first analysis result was obtained.

  Next, focusing on a part of the first substrate 12 and a part of the second substrate 14 shown in FIGS. 6A to 6D, each process performed by the microanalyzer manufacturing apparatus 100 according to the present embodiment will be described. Here, a part of the first substrate 12 and a part of the second substrate 14 are regions shown in the cross-sectional view between AA shown for convenience in FIG. 5.

  First, as shown in FIG. 6A, in the pattern formation processing unit 60, as in a general semiconductor manufacturing process, the thickness is about 30 μm through a known photolithography process, which is indicated by an arrow in FIG. A photosensitive polyimide precursor layer 16 in which the width (W) of the tubular channel 18 is about 10 μm is formed. In the present embodiment, the width of the tubular channel 18 is formed to be about 10 μm, but the present invention is not limited to this. Since the photosensitive polyimide precursor layer 16 of the present embodiment is formed through a photolithography process excellent in fine processing, the flexibility of the width of the tubular flow path 18 is high. Therefore, it can be said that the high degree of design freedom of the tubular flow path 18 greatly contributes to the enhancement of the performance of the microanalyzer when the analysis system is miniaturized and integrated.

  Next, the first substrate 12 on which the photosensitive polyimide precursor layer 16 is formed is introduced into the load lock chamber 40 of FIG. Thereafter, after the load lock chamber 40, the transfer chamber 50, the heating / pressurization chamber 20, and the alignment chamber 30 are exhausted, the first substrate 12 is sent to the heating / pressurization chamber 20 through the transfer chamber 50.

In the present embodiment, while exhausting by the pump 26, the valve 28 is opened, and nitrogen 250 L (liter) / min. Was introduced. At this time, the pressure in the chamber 21 is adjusted to be about 0.1 MPa (1 atm).
Thereafter, the oxygen concentration in the chamber 21 is controlled to be 50 ppm or less. In this embodiment, about 40 minutes after introducing nitrogen, the oxygen concentration in the chamber 21 became 6 ppm. After the oxygen concentration reaches 50 ppm or less, nitrogen is stably 150 L (liter) / min. be introduced. Introducing nitrogen gas into the chamber 21 improves the thermal conductivity of the heat applied to the photosensitive polyimide precursor layer 16 and, as a result, improves the in-plane uniformity of the heat treatment.

  After the oxygen concentration in the chamber 21 is controlled as described above, the heater in the stage 22 and the heater controller 24 raise the temperature of the stage 22 to 350 ° C. The first substrate 12 is continuously heated in this state for 1 hour and then cooled to room temperature. For convenience, this heat treatment is referred to as a first heat treatment. As a result of the first heat treatment, as shown in FIG. 6B, a photosensitive polyimide resin layer 17 that is heat-treated in an environment in which the oxygen concentration is controlled to 50 ppm or less is formed. The thickness of the photosensitive polyimide resin layer 17 was about 60% of the thickness of the photosensitive polyimide precursor layer 16 before heating.

  Here, the photosensitive polyimide resin layer 17 as a comparative example heated under the same conditions as the first heat treatment conditions except for the photosensitive polyimide resin layer 17 and the oxygen concentration in the air (about 20%). About two samples, the hardness of resin after a heating was measured with the dynamic micro hardness meter (the Shimadzu Corporation make, model number DUH-W201). As a result, although the detailed reason is not yet clear, the hardness of the photosensitive polyimide resin layer 17 that is heat-treated in an environment in which the oxygen concentration is controlled to 50 ppm or less is higher than that having an oxygen concentration of about 20%. It was found to be about 32% soft. Therefore, it is considered that the photosensitive polyimide resin layer 17 in the present embodiment is physically different from that which is heat-treated without controlling the oxygen concentration.

  In particular, the photosensitive polyimide resin layer as in this embodiment that was heat-treated in an environment where the oxygen concentration was controlled to 10 ppm or less had a light brown color on the surface after the heat treatment. On the other hand, the photosensitive polyimide resin layer whose oxygen concentration was not controlled had a substantially black surface color after the heat treatment. Even from this result, it is considered that the physical properties of the photosensitive polyimide resin layer are different.

  Next, after the chamber 21 is evacuated by the pump 26, the photosensitive polyimide resin layer 17 is sent to the alignment chamber 30 via the transfer chamber 50. In the alignment chamber 30, as shown in FIG. 6C, the other aligned second substrate 14 is bonded to the first substrate 12 from above, so that the microanalyzer 10 is formed.

  Thereafter, the microanalyzer 10 is sent again to the heating and pressurizing chamber 20 via the transfer chamber 50. In the heating and pressurizing chamber 20, as shown in FIGS. 3 and 6D, the microanalyzer 10 is pressurized at 32.7 MPa by the stage 22 and the pressing plate 23 that have reached a predetermined processing temperature.

Specifically, as shown in FIG. 7, first, the heating by the heater is started at time T _1. Temperature of the stage 22 and the pressing plate 23 reaches the 350 ° C. of maximum processing temperature after about 10 minutes from the start of heating, pressurizing treatment for micro analyzer 10 is started at time T _2. The pressure of 32.7 MPa on the microanalyzer 10 is made substantially instantaneously. Thereafter, the heating and pressurizing conditions for the microanalyzer 10 are continued for 15 minutes. That is, the temperature of the stage 22 and the pressing plate 23 is controlled to 350 ° C. or lower. Thereafter, pressure treatment is completed at time T _3, the micro analyzer 10 is slowly cooled. Then, all the processing is completed at time T ₄ the stage 22 and the pressing plate 23 is normal temperature (about 25 ° C.). For convenience, the above-described heating and pressure treatment is referred to as a second heat treatment. Note that the second heat treatment of the present embodiment was performed under a nitrogen atmosphere (pressure of about 0.1 MPa (1 atm)).

  Thereafter, the microanalyzer 10 is sent to the load lock chamber 40 via the transfer chamber 50 and taken out to the outside.

  As a result of each process described above, it was confirmed that the bonding strength of the microanalyzer 10 was good. Specifically, as a result of the peeling test of the microanalyzer 10, it was confirmed that the microanalyzer 10 was broken by pulling both sides of the microanalyzer 10 at 16.95 MPa. However, it has been found that this break is not a separation at the joint surface of the microanalyzer 10 but a break of the base material itself. Therefore, it became clear that the bonding strength exceeded the above-mentioned numerical value. Further, the thickness of the photosensitive polyimide resin layer 17 after the second heat treatment was substantially the same as the thickness after the first heat treatment. Specifically, that after the second heat treatment was only 2% lower than the thickness of the photosensitive polyimide resin layer after the first heat treatment. Thus, sufficient bonding strength was obtained even when the substrate was bonded at the same temperature as the heating temperature of the photosensitive polyimide resin. Moreover, since it turned out that the photosensitive polyimide resin layer 17 is equipped with the hardness of the grade which the thickness of the photosensitive polyimide resin layer 17 does not change substantially by the pressurization at the time of 2nd heat processing, It was confirmed that the apparatus and the method contribute to the improvement of the in-plane uniformity of the microanalyzer 10 that is initially formed by a semiconductor wafer-like substrate.

  Furthermore, as a result of bonding between glass (quartz, aluminosilicate glass, or soda glass) substrates under the same conditions as in this embodiment, almost no gas is emitted from the photosensitive polyimide resin, or compared with the conventional one. It was confirmed from the numerical change of the vacuum watch provided in the heating and pressurizing chamber 20 that it was significantly reduced.

  Here, as a comparative example, the microanalyzer 10 in which all the processes including the second heat treatment were performed under the same conditions as those of the first embodiment except for the concentration of oxygen in the air (about 20%). The bonding strength and the presence or absence of gas released from the resin were examined. As a result, it was confirmed that the sample of the comparative example subjected to the first heat treatment without controlling the oxygen concentration to 50 ppm or less was easily peeled to such an extent that it was not substantially joined. This is because the hardness of the photosensitive polyimide resin after the first heat treatment described above is harder than that in which the oxygen concentration is controlled, so the heating temperature during the second heat treatment is the first heat treatment. If it is the same as the heating temperature at this time, it is considered that sufficient bonding cannot be achieved. In other words, the photosensitive polyimide resin layer 17 after the first heat treatment of the present embodiment in which the oxygen concentration is controlled is formed in a state having some flexibility as compared with the comparative example. It is considered that sufficient bonding is ensured even at the same temperature as the first heat treatment temperature during the treatment. Therefore, the heat treatment of the photosensitive polyimide precursor layer 16 in an environment in which the oxygen concentration is controlled affects the bonding strength and the bonding state of the first substrate 12 and the second substrate 14 of the microanalyzer 10. Became clear.

  In the present embodiment, the oxygen concentration in the chamber 21 during the first heat treatment was 6 ppm. However, if the oxygen concentration is 50 ppm or less, more preferably 30 ppm or less, the photosensitive polyimide resin is cured. Therefore, imidization is hardly inhibited. In order not to cause the problem of poor bonding that may occur due to insufficient imidization, the above-described oxygen concentration is most preferably 10 ppm or less.

Further, in this embodiment, nitrogen gas is introduced into the chamber 21 in order to improve the thermal conductivity of the heat given to the photosensitive polyimide precursor layer 16 and increase the in-plane uniformity of the heat treatment. It is not limited. For example, instead of introducing nitrogen gas, a method of reducing the absolute amount of oxygen gas by increasing the pressure in the chamber 21 is also a modification of the present embodiment. In an experiment conducted by the inventors separately from the present embodiment, if the oxygen partial pressure is 9 × 10 ⁻⁴ Pa or less, the same effects as the present embodiment can be obtained with respect to the bonding strength and the gas released from the resin. It was confirmed that However, in consideration of the in-plane uniformity of the heat treatment substrate and the uniformity between the treatment substrates, it is preferable to introduce nitrogen gas.

<Second Embodiment>
FIG. 8 is a diagram showing conditions for the manufacturing process of the microanalyzer according to this embodiment. FIG. 8 corresponds to FIG. 7 of the first embodiment. The manufacturing method of the microanalyzer of the present embodiment is the same as that of the first embodiment, except for the pressurizing process for the microanalyzer during the second heat treatment described above. On the other hand, the microanalyzer manufacturing apparatus of the present embodiment has the same apparatus configuration as that of the first embodiment. Therefore, the description which overlaps with 1st Embodiment is abbreviate | omitted.

  As shown in FIG. 8, in the second heat treatment of the present embodiment, pressure is applied to the microanalyzer after the first heat treatment from before the temperature rise. Each process after the stage and the pressing plate reach 350 ° C. is the same as that in the first embodiment.

  The microanalyzer formed by each process of the present embodiment was slightly affected by the gas released from the resin as compared with the first embodiment. This is presumably because the gas that was not completely released during the first heat treatment even during the temperature rise during the second heat treatment was released during the second heat treatment stage. On the other hand, the bonding strength between the first substrate and the second substrate of the microanalyzer was substantially the same as that of the first embodiment. Further, the change in the thickness of the photosensitive polyimide resin before and after the second heat treatment was not different from the change in the first embodiment. Therefore, in order to further improve the quality of bonding, the pressurization start time for the microanalyzer is the time when the temperature of the stage and the pressing plate reaches the maximum temperature or immediately before (for example, 1 to 2 minutes before). It is preferable to start on.

<Third Embodiment>
FIG. 9 is a diagram showing conditions for the manufacturing process of the microanalyzer according to this embodiment. FIG. 9 corresponds to FIG. 7 of the first embodiment. The manufacturing method of the microanalyzer of this embodiment is the same as that of the first embodiment except for the maximum processing temperature in the first heat treatment and the second heat treatment described above. On the other hand, the microanalyzer manufacturing apparatus of the present embodiment has the same apparatus configuration as that of the first embodiment. Therefore, the description which overlaps with 1st Embodiment is abbreviate | omitted.

  The trade name of the photosensitive polyimide resin used in this embodiment is DURIMIDE (registered trademark) 7510. Moreover, the 1st heat processing temperature in this embodiment is 300 degreeC. Further, as shown in FIG. 9, the maximum processing temperature in the second heat treatment of the present embodiment is 300 ° C. The microanalyzer manufactured under the above processing conditions can also obtain a bonding strength substantially the same as that of the first embodiment. Also, the gas released from the photosensitive polyimide resin is almost completely eliminated or significantly reduced as compared with the conventional case, as in the first embodiment.

<Fourth Embodiment>
The manufacturing method of the microanalyzer of the present embodiment is the same as that of the first embodiment except that the oxygen concentration during the first heat treatment is 10 ppm. On the other hand, the microanalyzer manufacturing apparatus of the present embodiment has the same apparatus configuration as that of the first embodiment. Therefore, the description which overlaps with 1st Embodiment is abbreviate | omitted.

  As described above, even when the first heat treatment is performed in an environment where the oxygen concentration is 10 ppm, substantially the same bonding strength as in the first embodiment can be obtained. Also, the gas released from the photosensitive polyimide resin is almost completely eliminated or significantly reduced as compared with the conventional case, as in the first embodiment.

<Fifth Embodiment>
The manufacturing method of the microanalyzer of this embodiment is the same as that of the first embodiment except for the pressure applied to the microanalyzer during the second heat treatment described above. On the other hand, the microanalyzer manufacturing apparatus of the present embodiment has the same apparatus configuration as that of the first embodiment. Therefore, the description which overlaps with 1st Embodiment is abbreviate | omitted.

In embodiments other than those described above, if the microanalyzer is manufactured under a condition in which the pressure during the second heat treatment is changed, at least a part of each of the embodiments described above can be applied by pressurizing at 16.3 MPa or more and 49 MPa or less. It was confirmed that the effect of Specifically, when a surface area of a predetermined size (7500 mm ² ) or more contributes to bonding when pressed at a pressure of 16.3 MPa, the bonding strength should be comparable to that of the first embodiment. I understood. On the other hand, when a pressure of 49 MPa was applied, a phenomenon that a part of a fine pattern (1: 1 line and space) with a line width of 100 μm was crushed was confirmed. It turned out to be inferior to that of form. Also, it is confirmed that the gas released from the photosensitive polyimide resin is almost zero or significantly reduced as compared with the conventional case at any pressure of 16.3 MPa or 49 MPa. It was done.

  By the way, in each above-mentioned embodiment, although the 1st heat processing and the 2nd heat processing were performed in the same chamber, it is not limited to this. Even if the first heat treatment and the second heat treatment are performed in different chambers, the same effects as those of the present invention can be obtained.

  Moreover, in each above-mentioned embodiment, although the maximum temperature of 1st heat processing was 300 degreeC or 350 degreeC, it is not limited to this. If the maximum temperature of the first heat treatment is 200 ° C. or higher and 450 ° C. or lower, the second heat treatment temperature is set to the same or slightly lower temperature as described above, and at least some of the effects of the present invention can be obtained. It can be said that it is played. This is because if the temperature is lower than 200 ° C., a photosensitive polyimide resin suitable for bonding the substrates cannot be obtained. On the other hand, if the temperature exceeds 450 ° C., the photosensitive polyimide resin may be thermally decomposed. Because.

  In each of the above-described embodiments, the first heat treatment temperature and the second heat treatment temperature are set to the same temperature, but the second heat treatment temperature is set to a value 30 ° C. lower than the first heat treatment temperature. In addition, substantially the same effect as the present embodiment is achieved.

In each of the above-described embodiments, the second heat treatment is performed in a nitrogen atmosphere (pressure is about 0.1 MPa (1 atm)), but the present invention is not limited to this atmosphere. For example, even in an atmosphere of other inert gas (for example, argon gas) instead of nitrogen, substantially the same effect as the present embodiment can be obtained. Further, the pressure condition of the second heat treatment is not limited to about 0.1 MPa (1 atm). Even when the second heat treatment is performed under vacuum (for example, a pressure of 5 × 10 ⁻⁴ Pa), substantially the same effect as that of the present embodiment can be obtained.

  In the above-described embodiments, the material of the first substrate and the second substrate is silicon or Pyrex (registered trademark) glass, but is not limited thereto. The present invention does not require a glass material containing movable ions, metal, or the like as in anodic bonding, but provides a technique for bonding various substrates by using a photosensitive polyimide resin that has been subjected to a specific treatment. To do. For example, in terms of bonding of substrates, by applying the bonding technique in each of the above-described embodiments, bonding can be performed even between substrates on which silicon oxide films are formed or substrates on which silicon nitride films are formed. Can be done. In addition, even when an aluminum substrate and a glass substrate, a substrate and a glass substrate on which a silicon oxide film is formed, or a substrate and a glass substrate on which a silicon nitride film is formed are bonded by applying the present invention. sell. However, from the viewpoint of the visibility of specimens and reagents in the microanalyzer, at least one of the substrates is preferably a substrate with high transparency (for example, natural quartz, synthetic quartz, or aluminosilicate glass). In addition, from the viewpoint of manufacturing a reproducible microanalyzer by being immersed in an alkaline solution, natural quartz, synthetic quartz, and aluminosilicate glass, which are alkali-resistant substrates, are preferable.

  Furthermore, in terms of bonding of substrates, by applying the bonding technique in each of the above-described embodiments, a copper substrate, a copper substrate and a silicon substrate, a substrate on which a copper substrate and a silicon oxide film are formed, a sapphire substrate Even a silicon substrate, a sapphire substrate, a substrate on which a silicon oxide film is formed, or a quartz plate can be bonded. As described above, modifications that exist within the scope of the present invention are also included in the claims.

  The present invention is widely used as various microanalyzers and elemental technologies thereof, and can be widely used as a device for manufacturing microanalyzers.

It is a top view of the manufacturing apparatus of the microanalyzer in one embodiment of the present invention. It is sectional drawing at the time of the 1st heat processing in the heating and pressurizing chamber which is a part of manufacturing apparatus of the microanalyzer in one embodiment of the present invention. It is sectional drawing at the time of the 2nd heat processing in the heating and pressurizing chamber shown in FIG. It is a top view of the microanalyzer in one embodiment of the present invention. FIG. 5 is an enlarged view of a part (Z portion) of FIG. 4. It is a schematic diagram explaining the manufacturing process flow of the microanalysis apparatus in one embodiment of this invention. It is a schematic diagram explaining the manufacturing process flow of the microanalysis apparatus in one embodiment of this invention. It is a schematic diagram explaining the manufacturing process flow of the microanalysis apparatus in one embodiment of this invention. It is a schematic diagram explaining the manufacturing process flow of the microanalysis apparatus in one embodiment of this invention. It is a figure which shows the conditions of the manufacturing process of the microanalysis apparatus in one embodiment of this invention. It is a figure which shows the conditions of the manufacturing process of the microanalysis apparatus in other embodiment of this invention. It is a figure which shows the conditions of the manufacturing process of the microanalysis apparatus in other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Microanalyzer 12 1st board | substrate 14 2nd board | substrate 16 Photosensitive polyimide precursor layer 17 Photosensitive polyimide resin layer 18 Tubular flow path 19a Injection | emission opening part 19b Discharge opening part 20 Heating and pressurization chamber 21 Chamber 22 Stage 23 Press plate 24, 25 Heater control unit 26 Pump 27 Nitrogen gas cylinder 28 Valve 30 Alignment chamber 40 Load lock chamber 50 Transfer chamber 60 Pattern formation processing unit 100 Microanalyzer manufacturing apparatus

Claims (8)

Forming a photosensitive polyimide precursor layer on the first substrate;
A pattern forming step of forming a pattern of the photosensitive polyimide precursor layer;
After the first heating step of forming the photosensitive polyimide resin layer by heating the photosensitive polyimide precursor layer on which the pattern is formed at 200 ° C. or higher and 350 ° C. or lower in an environment where the oxygen concentration is 50 ppm or lower, Sandwiching the photosensitive polyimide resin layer between two substrates and the first substrate;
While pressing the first substrate and the second substrate at 16.3 MPa or more and 49 MPa or less, the difference between the same temperature as the maximum temperature of the first heating step or the maximum temperature of the first heating step is within 30 ° C. And a second heating step of heating at a temperature lower than the maximum temperature of the first heating step. The method for manufacturing a microanalyzer according to claim 1, wherein the gas other than oxygen in the first heating step is substantially composed of nitrogen. 2. The method for manufacturing a microanalyzer according to claim 1, wherein the second heating step starts when or after the pressurization to the first substrate and the second substrate reaches the maximum temperature of the second heating step. . The first substrate and the second substrate are joined by sandwiching the patterned photosensitive polyimide resin layer as an adhesive layer,
The microanalyzer in which the first substrate, the second substrate, and the photosensitive polyimide resin layer form a tubular flow path. A pattern formation processing unit for forming a pattern of the photosensitive polyimide precursor layer on the first substrate;
A first heat treatment unit that forms a photosensitive polyimide resin layer by heating the photosensitive polyimide precursor layer on which the pattern is formed at 200 ° C. or higher and 350 ° C. or lower in an environment where the oxygen concentration is 50 ppm or less;
A bonding portion for bonding the first substrate and the second substrate with the photosensitive polyimide resin layer interposed therebetween;
While pressurizing the first substrate and the second substrate at 16.3 MPa or more and 49 MPa or less, the difference between the same temperature as the maximum processing temperature of the first heat processing unit or the maximum processing temperature of the first heat processing unit is An apparatus for manufacturing a microanalyzer, comprising: a second heat treatment unit that heats at a temperature lower than a maximum treatment temperature of the first heat treatment unit within 30 ° C. The apparatus for manufacturing a microanalyzer according to claim 5, wherein the gas other than oxygen in the first heat treatment unit is substantially composed of nitrogen. The said 2nd heat processing part starts when the pressurization with respect to a said 1st board | substrate and a said 2nd board | substrate reaches | attains the maximum temperature of the said 2nd heat processing part, or it starts after that. Manufacturing equipment for microanalyzers. The first substrate, the second substrate of the microanalyzer in which the alkali-resistant first substrate and the alkali-resistant second substrate are bonded by sandwiching the photosensitive polyimide resin layer on which the pattern is formed as an adhesive layer, And a step of immersing the microanalyzer in an alkaline solution after the fluid has flowed at least once in the tubular flow path formed by the photosensitive polyimide resin layer.

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